Liquid crystal compounds having substituted alkyl groups, liquid crystal composition and liquid crystal display element

ABSTRACT

The present invention provides liquid crystalline compounds having compatibility with the other liquid crystal materials and excellent stability, and having low viscosity and high transition temperature of the isotropic phase, liquid crystal compositions containing at least one kind of the liquid crystalline compounds, and liquid crystal display devices constituted by using the liquid crystal compositions. The liquid crystalline compounds are represented by the following formula: 
     
       
         R—A 1 —Z 1 —A 2 —Z 2 —A 3 —Z 3 —A 4 —(CH 2 ) m .X  (1) 
       
     
     wherein R indicates H or an alkyl group having 1 to 10 carbon atoms (one or more methylene group (—CH 2 —) in the alkyl group may be replaced by —O—, —S—, —CO—, —CH═CH— or —C≡C—, but —O— or —S— are not continuous), m indicates an integer of 1 to 10; X indicates F, Cl, Br, I or OH; A 1 , A 2 , A 3  and A 4 , each independently, indicate a trans-1,4-cyclohexylene group, a 1,4-phenylene group in which one or more hydrogen atoms on the ring may be substituted by a fluorine atom, a cyclohexenylenediyl group, a pyrimidine-2,5-diyl group, a pyridine-2,5-diyl group or a 1,3-dioxane-2,5-diyl group; Z 1 , Z 2  and Z 3 , each independently, indicate —(CH 2 ) 2 — or a covalent bond, and at least two of Z 1 , Z 2  and Z 3  indicate covalent bonds.

TECHNICAL FIELD

The present invention relates to a liquid crystalline compound and aliquid crystal composition, more particularly, it relates to a newliquid crystalline compound having substituted alkyl groups, a liquidcrystal composition containing the liquid crystalline compound, and aliquid crystal display device constituted by using the liquid crystalcomposition.

BACKGROUND ART

Liquid crystal devices using liquid crystalline compounds (in thepresent specification, the term of the liquid crystalline compound isused as a generic name of the compound showing liquid crystal phases andthe compound not showing liquid crystal phases but useful as ingredientsof the liquid crystal compositions) are broadly used in displays ofclocks, watches and electronic calculators, word processors and thelike. To these display devices, an optical anisotropy, a dielectricanisotropy and the like of the liquid crystalline compound are applied.

As the liquid crystal phases, a nematic liquid crystal phase, a smecticliquid crystal phase, and a cholesteric liquid crystal phase are used,and particularly, the nematic liquid crystal phase is broadly utilized.As display modes, there are a dynamic scatter (DS) type, a deformationtype of an aligning phase (DAP), a guest/host (GH) type, a twistednematic (TN) type, a super twisted nematic (STN) type, a thin filmtransistor (TFT) type and the like.

Although the liquid crystalline compounds used in these display modesmust show liquid crystal phases at broad temperature ranges, mainly atroom temperature, they must be sufficiently stable under conditions thatthe display devices are used, and they must have characteristics enoughto drive the display devices, a single liquid crystalline compoundsatisfying these conditions is still not found. For these reasons, a fewkinds or several tens of kinds of liquid crystalline compounds areconventionally mixed to prepare the liquid crystal compositionssatisfying desired properties. It is required that these liquid crystalcompositions are stable to moisture, light, heat and air which exist innormal conditions using the display devices, stable to electric fieldand electromagnetic radiation, and chemically stable to mixed compounds.Further, it is required that these liquid crystal compositions showproper valuer physical properties such as a refractive index anisotropyvalue (Δ n) and a dielectric anisotropy value (Δ ε) of the liquidcrystal compositions dictate the display modes or the forms of thedisplay devices. Further, it is important that each ingredient of theseliquid crystal compositions has mutually good solubility.

In recent years, various environment using the liquid crystal devicesrequires the liquid crystal compositions showing liquid crystal phasesat a higher temperature. To achieve the requirement, the ingredient maybe constituted from the compounds having high transition temperature ofan isotropic phase. Such compounds are known from the compoundsrepresented by formula (a) of Japanese Patent Publication No. 62-46527and formula (b) of Japanese patent Publication No. 4-28693.

These compounds have a high transition temperature of an isotropic phaseand relatively low viscosity, but the compounds have problems that thecompatibility with the other ingredients in the composition is notenough, so that the compounds should be used in limited amounts.

Objects of the present invention are to solve the problems of the aboveconventional techniques, and to provide liquid crystalline compoundshaving excellent compatibility with the other liquid crystal materialsand stability, low viscosity, and a high transition temperature of anisotropic phase; liquid crystal compositions comprising the compoundsand liquid crystal devices constituted by using the liquid crystalcompositions.

DISCLOSURE OF INVENTION

For achieving the above objects, the present invention is as follows.

(1) A liquid crystalline compound which is represented by generalformula (1):

R—A₁—Z₁—A₂—Z₂—A₃—Z₃—A₄—(CH₂)_(m).X  (1)

wherein R indicates H or an alkyl group having 1 to 10 carbon atoms (oneor more methylene groups (—CH₂—) in the alkyl group may be replaced by—O—, —S—, —CO—, —CH═CH— or —C≡C—, but —O— or —S— are not continuous), mindicates an integer of 1 to 10; X indicates F, Cl, Br, I or OH; A₁, A₂,A₃ and A₄, each independently, indicate a trans-1,4-cyclohexylene group,a 1,4-phenylene group in which one or more hydrogen atoms on the ringmay be substituted by a fluorine atom, a cyclohexenylenediyl group, apyrimidine-2,5-diyl group, a pyridine-2,5-diyl group or a1,3-dioxane-2,5-diyl group; Z₁, Z₂ and Z₃, each independently, indicate—(CH₂)₂— or a covalent bond, and at least two of Z₁, Z₂ and Z₃ indicatecovalent bonds.

(2) A liquid crystalline compound according to (1), wherein X is F.

(3) A liquid crystalline compound according to (1), wherein X is OH.

(4) A liquid crystalline compound according to (2), wherein Z₁, Z₂ andZ₃ are covalent bonds.

(5) A liquid crystalline compound according to (2), wherein Z₁ is—(CH₂)₂—.

(6) A liquid crystalline compound according to (2), wherein Z₂ is—(CH₂)₂—.

(7) A liquid crystalline compound according to (2), wherein Z₃ is-(CH₂)2-.

(8) A liquid crystalline compound according to (4), wherein both A₁ andA₄ are the trans 1,4-cyclohexylene group, and both A₂ and A₃ are the1,4-phenylene group in which one or more hydrogen atoms on the ring maybe substituted by a fluorine atom.

(9) A liquid crystalline compound according to (4), wherein both A₁ andA₂ are the 1,4-phenylene group in which one or more hydrogen atoms onthe ring may be substituted by a fluorine atom, and both A₃ and A₄ arethe trans 1,4-cyclohexylene group.

(10) A liquid crystalline compound according to (6), wherein both A₁ andA₂ are the 1,4-phenylene group in which one or more hydrogen atoms onthe ring may be substituted by a fluorine atom, and both A₃ and A₄ arethe trans 1,4-cyclohexylene group.

(11) A liquid crystal composition comprising at least one of liquidcrystalline compounds according to any one of (1) to (10).

(12) A liquid crystal composition, characterized in that it comprises asthe first constituent at least one compound selected from the groupconsisting of the liquid crystalline compounds described in any one of(1) to (10), and as the second constituent at least one compoundselected from the group consisting of the compounds represented bygeneral formulas (2), (3) and (4):

wherein R₁ indicates an alkyl group having 1 to 10 carbon atoms; X₁indicates F, Cl, OCF₃, OCF₂H, CF₃, CF₂H or CFH₂; L₁, L₂, L₃ and L₄, eachindependently indicate H or F; Z₄ and Z₅, each independently indicate—(CH₂)₂—, —CH═CH— or a covalent bond, and a indicates 1 or 2.

(13) A liquid crystal composition, characterized in that it comprises asthe first constituent at least one compound selected from the groupconsisting of the liquid crystalline compounds described in any one of(1) to (10), and as the second constituent at least one compoundselected from the group consisting of the compounds represented bygeneral formulas (5), (6), (7), (8) and (9):

wherein R₂ indicates F, an alkyl group having 1 to 10 carbon atoms or analkenyl group having 2 to 10 carbon atoms; any methylene group (—CH₂—)in the alkyl group or the alkenyl group may be replaced by an oxygenatom(—O—), but two or more methylene groups are not continuouslyreplaced by the oxygen atom; ring A indicates a trans-1,4-cyclohexylenegroup, a 1,4-phenylene group or a 1,3-dioxane-2,5-diyl group; ring Bindicates a trans-1,4-cyclohexylene group, a 1,4-phenylene group or apyrimidine-2,5-diyl group; ring C indicates a trans-1,4-cyclohexylenegroup or a 1,4-phenylene group; Z₆ indicates —(CH₂)₂—, —COO— or acovalent bond; L₅ and L₆, each independently, indicate H or F; and b andc, each independently, indicate 0 or 1,

wherein R₃ indicates an alkyl group having 1 to 10 carbon atoms, L₇indicates H or F, and d indicates 0 or 1,

wherein R₄ indicates an alkyl group having 1 to 10 carbon atoms; ring Dand ring E, each independently, indicate trans-1,4-cyclohexylene groupor a 1,4-phenylene group; Z₇ and Z₈, each independently, indicate -COO-or a covalent bond; Z₉ indicates —COO— or —C≡C—; L₈ and L₉, eachindependently, indicate H or F; X₂ indicates F, OCF₃, OCF₂H, CF₃, CF₂Hor CFH₂, when X₂ indicates OCF₃, OCF₂H, CF₃, CF₂H or CFH₂, L₈ and L₉both indicate H; e, f and g, each independently, indicate 0 or 1,

wherein R₅ and R₆, each independently, indicate an alkyl group having 1to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, andin any case, any methylene group (—CH₂—) may be replaced by an oxygenatom (—O—), but two or more methylene groups are not continuouslyreplaced by an oxygen atom; ring G indicates a trans-1,4-cyclohexylenegroup, a 1,4-phenylene group or a pyrimidine-2,5-diyl group; ring Hindicates a trans-1,4-cyclohexylene group or a 1,4-phenylene group; Z₁₀indicates —C≡C—, —COO—, —(CH₂)₂—, —CH═CH—C≡C— or a covalent bond; Z₁₁indicates —COO— or a covalent bond, and

wherein R₇ and R₈, each independently, indicate an alkyl group having 1to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, andin any case, any methylene group (—CH₂—) may be replaced by an oxygenatom (—O—), but two or more methylene groups are not continuouslyreplaced by an oxygen atom; ring I indicates a trans-1,4-cyclohexylenegroup, a 1,4-phenylene group or a pyrimidine-2,5-diyl group; ring Jindicates a trans-1,4-cyclohexylene group, a 1,4-phenylene group inwhich one or more hydrogen atoms on the ring may be substituted by afluoric atom, or a pyrimidine-2,5-diyl group; ring K indicates atrans-1,4-cyclohexylene group or a 1,4-phenylene group, Z₁₂ and Z₁₄,each independently, indicate —COO—, —(CH₂)₂— or a covalent bond, Z₁₃indicates —CH═CH—, —C≡C—, —COO— or a covalent bond; and h indicates 0 or1.

(14) A liquid crystal composition, characterized in that it comprises asthe first constituent at least one compound selected from the groupconsisting of the liquid crystalline compounds described in any one of(1) to (10), and as a part of the second constituent at least onecompound selected from the group consisting of the compounds representedby general formulas (2), (3) and (4), and the other part of the secondconstituent at least one compound selected from the group consisting ofthe compounds represented by general formulas (5), (6), (7), (8) and(9).

(15) A liquid crystal display device constituted by using the liquidcrystal compositions described in any one of (1) to (14).

The liquid crystalline compounds represented by general formula (1) inthe present invention have excellent compatibility with the other liquidcrystal materials, and a high transition temperature of an isotropicphase. These compounds do not show increase of viscosity by introductionof substituted alkyl groups. Further, these liquid crystalline compoundsare physically and chemically stable under conditions using commonlydisplay devices. In addition, by appropriate selection of six-memberedrings, substituted groups and/or bond groups from molecularconstituents, it is possible to obtain a compound having desiredphysical properties. Accordingly, when the compounds of the presentinvention are used as ingredients of liquid crystal compositions, it ispossible to provide new liquid crystal compositions having preferablecharacteristics.

The compounds represented by general formula (1) in the presentinvention are classified as follows:

In the following formulas, Q indicates —(CH₂)_(m)—X, wherein m indicatesthe same meaning as described above. Cyc indicates atrans-1,4-cyclohexylene group, Phe indicates a 1,4-phenylene group, Hexindicates a cyclohexenylenediyl group, Pyr indicates apyrimidine-2,5-diyl group, Pyd indicates a pyridine-2,5-diyl group, Dioindicates a 1,3-dioxane-2,5-diyl group, and one or more hydrogen atomsof the above Phe may be substituted by fluorine atoms; A₁, A₂, A₃ and A₄are selected from Cyc, Phe, Hex, Pyr, Pyd or Dio, preferably, there arenot two or more hetero rings.

R-A₁-A₂-A₃-A₄-Q (1a) R-A₁-(CH₂)₂-A₂-A₃-A₄-Q (1b) R-A₁-A₂-(CH₂)₂-A₃-A₄-Q(1c) R-A₁-A₂-A₃-(CH₂)₂-A₄-Q (1d)

The compounds represented by formula (1a) are developed into thecompounds represented by the following formulas (1aa)-(1ap).

R-Cyc-Cyc-Cyc-Cyc-Q (1aa) R-Cyc-Cyc-Cyc-Phe-Q (1ab) R-Cyc-Cyc-Phe-Phe-Q(1ac) R-Cyc-Phe-Phe-Phe-Q (1ad) R-Phe-Phe-Phe-Phe-Q (1ae)R-Phe-Phe-Phe-Cyc-Q (1af) R-Phe-Phe-Cyc-Cyc-Q (1ag) R-Phe-Cyc-Cyc-Cyc-Q(1ah) R-Cyc-Cyc-Phe-Cyc-Q (1ai) R-Cyc-Phe-Phe-Cyc-Q (1ak)R-Phe-Phe-Cyc-Phe-Q (1al) R-Hex-Phe-Phe-Hex-Q (1am) R-Phe-Pyr-Phe-Cyc-Q(1an) R-Dio-Cyc-Phe-Phe-Q (1ao) R-Pyr-Phe-Cyc-Cyc-Q (1ap)

The compounds represented by formula (1b) are developed into thecompounds represented by the following formulas (1ba)-(1bp).

R-Cyc-(CH₂)₂-Cyc-Cyc-Cyc-Q (1ba) R-Cyc-(CH₂)₂-Cyc-Cyc-Phe-Q (1bb)R-Cyc-(CH₂)₂-Cyc-Phe-Phe-Q (1bc) R-Cyc-(CH₂)₂-Phe-Phe-Phe-Q (1bd)R-Phe-(CH₂)₂-Phe-Phe-Phe-Q (1be) R-Phe-(CH₂)₂-Phe-Phe-Cyc-Q (1bf)R-Phe-(CH₂)₂-Phe-Cyc-Cyc-Q (1bg) R-Phe-(CH₂)₂-Cyc-Cyc-Cyc-Q (1bh)R-Cyc-(CH₂)₂-Cyc-Phe-Cyc-Q (1bi) R-Cyc-(CH₂)₂-Phe-Cyc-Cyc-Q (1bj)R-Cyc-(CH₂)₂-Phe-Phe-Cyc-Q (1bk) R-Phe-(CH₂)₂-Phe-Cyc-Phe-Q (1bl)R-Phe-(CH₂)₂-Cyc-Phe-Phe-Q (1bm) R-Phe-(CH₂)₂-Cyc-Cyc-Phe-Q (1bn)R-Cyc-(CH₂)₂-Cyc-Phe-Pyd-Q (1bo) R-Cyc-(CH₂)₂-Cyc-Cyc-Dio-Q (1bp)

The compounds represented by formula (1c) are developed into thecompounds represented by the following formulas (1ca)-(1cp).

R-Cyc-Cyc-(CH₂)₂-Cyc-Cyc-Q (1ca) R-Cyc-Cyc-(CH₂)₂-Cyc-Phe-Q (1cb)R-Cyc-Cyc-(CH₂)₂-Phe-Phe-Q (1cc) R-Cyc-Phe-(CH₂)₂-Phe-Phe-Q (1cd)R-Phe-Phe-(CH₂)₂-Phe-Phe-Q (1ce) R-Phe-Phe-(CH₂)₂-Phe-Cyc-Q (1cf)R-Phe-Phe-(CH₂)₂-Cyc-Cyc-Q (1cg) R-Phe-Cyc-(CH₂)₂-Cyc-Cyc-Q (1ch)R-Cyc-Cyc-(CH₂)₂-Phe-Cyc-Q (1ci) R-Cyc-Phe-(CH₂)₂-Cyc-Cyc-Q (1cj)R-Cyc-Phe-(CH₂)₂-Phe-Cyc-Q (1ck) R-Phe-Phe-(CH₂)₂-Cyc-Phe-Q (1cl)R-Phe-Cyc-(CH₂)₂-Phe-Phe-Q (1cm) R-Phe-Cyc-(CH₂)₂-Cyc-Phe-Q (1cn)R-Dio-Cyc-(CH₂)₂-Phe-Phe-Q (1co) R-Hex-Phe-(CH₂)₂-Phe-Cyc-Q (1cp)

The compounds represented by formula (1d) are developed into thecompounds represented by the following formulas (1da)-(1dp).

R-Cyc-Cyc-Cyc-(CH₂)₂-Cyc-Q (1da) R-Cyc-Cyc-Cyc-(CH₂)₂-Phe-Q (1db)R-Cyc-Cyc-Phe-(CH₂)₂-Phe-Q (1dc) R-Cyc-Phe-Phe-(CH₂)₂-Phe-Q (1dd)R-Phe-Phe-Phe-(CH₂)₂-Phe-Q (1de) R-Phe-Phe-Phe-(CH₂)₂-Cyc-Q (1df)R-Phe-Phe-Cyc-(CH₂)₂-Cyc-Q (1dg) R-Phe-Cyc-Cyc-(CH₂)₂-Cyc-Q (1dh)R-Cyc-Cyc-Phe-(CH₂)₂-Cyc-Q (1di) R-Cyc-Phe-Cyc-(CH₂)₂-Cyc-Q (1dj)R-Cyc-Phe-Phe-(CH₂)₂-Cyc-Q (1dk) R-Phe-Phe-Cyc-(CH₂)₂-Phe-Q (1dl)R-Phe-Cyc-Phe-(CH₂)₂-Phe-Q (1dm) R-Phe-Cyc-Cyc-(CH₂)₂-Phe-Q (1dn)R-Cyc-Phe-Cyc-(CH₂)₂-Phe-Q (1do) R-Cyc-Dio-Phe-(CH₂)₂-Phe-Q (1dp)

In the above all compounds, Q is a ω-substituted alkyl group,preferably, fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl,5-fluoropentyl, 6-fluorohexyl, 10-fluorodecyl, chloromethyl,2-chloroethyl, 3-chloropropyl, 4-chlorobutyl, 5-chloropentyl,6-chlorohexyl, 9-chlorononyl, bromomethyl, 2-bromoethyl, 3-bromopropyl,4-bromobutyl, 5-bromopentyl, 6-bromohexyl, 8-bromooctyl, iodomethyl,2-iodoethyl, 3-iodopropyl, 4-iodobutyl, 5-iodopentyl, 6-iodohexyl,7-iodoheptyl, hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl,4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl or 10-hydroxydecyl.

As shown in the above, the compounds represented by formulas(1aa)-(1ap), (1ba)-(1bp), (1ca)-(1cp) and (1da)-(1dp) are preferablecompounds. Most preferably, the compounds represented by the followingformulas (1-1)-(1-44) are exemplified.

(1-1)

(1-2)

(1-3)

(1-4)

(I-5)

(I-6)

(I-7)

(I-8)

(I-9)

(I-10)

(I-11)

(I-12)

(I-13)

(I-14)

(I-15)

(I-16)

(I-17)

(I-18)

(I-19)

(I-20)

(I-21)

(I-22)

(I-23)

(I-24)

(I-25)

(I-26)

(I-27)

(I-28)

(I-29)

(I-30)

(I-31)

(I-32)

(I-33)

(I-34)

(I-35)

(I-36)

(I-37)

(I-38)

(I-39)

(I-40)

(I-41)

(I-42)

(I-43)

(I-44)

The liquid crystalline compounds represented by general formula (1) inthe present invention can be prepared by well-known common organicsynthetic methods, for example, by the following process.

Namely, compound (1) that X is OH in formula (1) can be treated with afluorinating agent such as diethylamino sulfur trifluoride (DAST) (M.Hudlicky, Organic Reactions, 35, 513 (1988), P. A. Messina et al., TheJournal of Fluorine Chemistry, 42, 137 (1989)),(2-chloro-1,1,2-trifluoroethyl)diethylamine (C. M. Sharts et al.,Organic Reactions, 21, 158 (1974)), molpholino sulfur trifluoride (K. C.Mange et al., The Journal of Fluorine Chemistry, 43, 405 (1989)) ordiethylamine-hexafluoropropene (Ishikawa et al., Bulletin of theChemical Society of Japan, 52 (11), 3377 (1979)), to produce compound(2) that X is F in formula (1).

Compound (2) also can be obtained by reaction of the above alcohol (1)with a halogenation agent such as hydrogen chloride/zinc chloride,hydrobromic acid, hydroiodic acid, thionyl chloride, thionyl bromide,potassium iodide, phosphorus triiodide, phosphorus trichloride,phosphorus tribromide, phosphorus pentachloride or phosphorusoxychloride, and further, by reaction of compound (3) that X is ahalogen atom in formula (1) with a fluorinating agent such as KF(Ishikawa et al., Chemistry Letters, 761 (1981)), pyridynium poly(hydrogen fluoride) (HF—Py) (G. A. Olah et al., The Journal of OrganicChemistry, 44, 3872 (1979)),n-Bu₄NF (D. O. Kiesewetter et al., TheJournal of Organic Chemistry, 49, 4900 (1984)) or a Ph₄PF—HF complex (S.J. Brown et al., Journal of the Chemical Society ChemicalCommunications, 672 (1985)).

Moreover, after changing the above alcohol (1) is into silyl ether (4),the above compound (2) can be produced by fluorination of silyl ether(4) with a fluorinating agent such as PhPF₄ (H. Koop et al., Journal ofFluorine Chemistry, 1, 252 (1972), n-Bu₄NF/CH₃SO₂F or DAST and the like.

The above alcohol (1) which is a starting material can be produced by awell-known common organic synthetic process, for example, it is easilyobtained by the following methods as shown in scheme 1-12.

In each scheme, n₁ and n₂, each independently, indicates 0 or

Reaction conditions: 1, and X′ indicates Br or I.

a) halide/n-BuLi b) —H₂O/acid catlyst c) H₂/Pd-C d) I₂/SbCl₅ e)halide/n-BuLi/ZnCl₂ f) H⁺ g) (EtO)₂POCH₂COOEt/base h) LAH i) HBr j)cyclohexanone derivative/n-Buli k) PCC l) halide/Mg m)

n) Me₃SiI o) Ru-C

Namely, as shown in scheme 1, after compound (5) is changed intocompound (6) by the method of J. D. Buhler et al. described in TheJournal of Organic Chemistry, 38, 904 (1973)) or the method of Imamotoet al. described in Journal of the American Chemical Society, 111, 4392(1989)), compound (7) is obtained by heating and dehydration in asolvent such as toluene or xylene in the presence of an acidic catalystsuch as p-toluenesulfonic acid. After compound (7) is changed intocompound (8) by catalytic hydrogenation in the presence of a catalystsuch as Pd—C, halide (9) is obtained by a method of Uemura et al.,Bulletin of the Chemical Society of Japan, 47, 147 (1974) or a method ofH. Becker et al, Organikum, VEB Deutscher Verlag der Wissenschaften, 189(1973)).

After compound (9) is treated by cross coupling reaction of a method ofHayashi et al.(Journal of the American Chemical Society, 106, 158(1984)) or a method of Negishi et al. (The Journal of Organic Chemistry,42 (10), 1821 (1977)), compound (11) of an example of an alcoholderivative is obtained by deprotection.

In addition, after a Grignard reagent or a lithium reagent of compound(9) is prepared, it is reacted with formaldehyde, or a cyclic ether ofethyleneoxide or propyleneoxide, corresponding alcohol derivatives areobtained, respectively.

Then, as shown in scheme 2, after compound (5) is changed into compound(12) by a method of W. S. Wardsworth et al. (Journal of the AmericanChemical Society, 83, 1733 (1961), it is reacted by catalytichydrogenation to obtain compound (13). Then, the resulting compound (13)is reduced with a reducing agent such as lithium aluminum hydride (LAH),bis(2-methoxyethoxy)aluminum sodium hydride, boron lithium hydride ordiisobuthyl aluminum hydride to obtain compound (4).

Said compound (14) is changed to a halide (15) by a method of those ofH. Becker et al. (Organikum, VEB Deutscher Verlag der Wissenschaften,212 (1973), C. R. Noller et al. (Organic Synthesis, II, 358 (1943)), G.A. Wiley et al. (Journal of the American Chemical Society, 86, 964(1964)), S. Manna et al. (Synthetic Communications, 15, 633 (1985)), G.Cainelli et al. (Synthesis, 306 (1983)), G. H. Daub et al. (The Journalof Organic Chemistry, 19, 1571 (1954)), H. Stone et al. (OrganicSynthesis, IV, 323 (1963)), G. A. Olah et al. (Synthesis, 653 (1974),The Journal of Organic Chemistry, 44, 1247 (1979)), Imamoto et al.(Synthesis, 460 (1983)) and the like; a cross coupling method such as amethod of Hayashi et al., and halogenation of a method of Uemura et al.,and a cross coupling method of Hayashi et al. are conducted; theresulting product are deprotected to obtain compound (17) as an exampleof alcohol derivatives.

Further, as shown in scheme 3, said compound (15) is reacted intocompound (18) as an example of alcohol derivatives through the steps ofthe method of aforementioned J. D. Buhler et al., dehydration, catalytichydrogenation, halogenation by the method of Uemura et al., and crosscoupling by the method of Hayashi et al., and deprotection.

As shown in scheme 4, compound (19) obtained by a method of W. Sucrow etal. (Chemische Berichte, 121, 219 (1988)) is oxidized with an oxidizingagent such as pyridinium chlorochromate (PCC), pyridinium dichromate,pyridinium fluorochromate, chromium oxide, activated manganese dioxideor dimethyl sulfoxide/oxaryl chloride to obtain compound (20).

Then, compound (20) is reacted with phenyl magnesium halide of aGrignard reagent, dehydrated, reacted by catalytic hydrogenation, byhalogenation of the above method of Uemura et al, by a cross couplingreaction of the above method of Hayashi et al., and by deprotection toobtain compound (22) which is an example of alcohol derivatives.

Moreover, as shown in scheme 5, the above compound (20) is reacted bythe above method of W. S. Wardsworth et al., by catalytic hydrogenation,by reduction, and by the above method of H. Becker et al. to obtaincompound (23). Then, after the cross coupling reaction of Hayashi etal., halogenation by the method of Uemura et al., and cross coupling bythe method of Hayashi et al., the resulting compound can be deprotectedto obtain compound (24) of the example of alcohol derivatives.

Moreover, as shown in scheme 6, compound (25) is changed into compound(27) through the steps of the method of aforementioned J. D. Buhler etal., dehydration, catalytic hydrogenation and deprotection. Then, aftercompound (27) is reacted by Wittig reaction (G. Wittig et al.,Angewandte Chemie, 71, 121, 1373 (1959), Organic Reactions, Vol. 14,Chapter 3) and catalytic hydrogenation, the resulting compound can bedeprotected to obtain compound (28) as an example of alcoholderivatives.

Further, as shown in scheme 7, after compound (25) is reacted by thecross coupling reaction of Hayashi et al., deprotection, a Wittigreaction and catalytic hydrogenation, the resulting compound can bedeprotected to obtain compound (29) as an example of alcoholderivatives.

As shown in scheme 8, compound (30) is reacted by the method of J. D.Buhler et al to obtain compound (31). Compound (31) is reacted bydehydration, catalytic hydrogenation, deprotection, a Wittig reactionand catalytic hydrogenation, and the resulting compound is deprotectedto obtain compound (32) as an example of alcohol derivatives.

As shown in scheme 9, after compound (33) is changed into compound (34)by the method of J. D. Buhler et al. and the compound is changed intocompound (35) by dehydration and deprotection with iode trimethylsilane, boron trifluoride or the like. Compound (35) is reacted bycatalytic hydrogenation in the presence of a catalyst such as Ru—C andoxidized to obtain compound (36).

After repeating the reaction from compound (33) to compound (36) toobtain a cyclohexanone derivative, the derivative is reacted by theWittig reaction and catalytic hydrogenation, and the resulting compoundcan be deprotected to obtain compound (37) as an example of alcoholderivatives.

Moreover, as shown in scheme 10, after compound (38) is reacted by themethod of J. D. Buhler et al., dehydration, catalytic hydrogenation,deprotection, the Wittig reaction and catalytic hydrogenation, theresulting compound can be deprotected to obtain compound (40) as anexample of alcohol derivatives.

As shown in scheme 11, after compound (41) is reacted by the crosscoupling method of Hayashi et al., deprotection and the Wittig reaction,the resulting compound can be deprotected to obtain compound (43) as anexample of alcohol derivatives.

Further, as shown in scheme 12, the above compound (41) is reacted bythe cross coupling method of Hayashi et al., halogenation of the methodof Uemura and the cross coupling method of Hayashi et al, and then theresulting compound can be deprotected to obtain compound (45) as anexample of alcohol derivatives.

Compounds of the present invention other than the above-mentionedexamples, for example, the compounds substituting hydrogen atoms forfluorine atoms in aromatic rings, can be produced by the above methodsor combinations of these methods.

The liquid crystalline compounds of the present invention obtained bythe above methods have excellent compatibility with other liquid crystalmaterials and a high transition temperature of an isotropic phase, andan increase in viscosity is not found by introduction of substitutedalkyl groups. Since they have excellent stability, these compounds canbe used as excellent ingredients constituting the nematic liquid crystalcompositions.

Hitherto, it is known that, when the hydrogen atoms in molecules of aliquid crystalline compound are substituted by fluorine atoms, there aredisadvantages that the transition temperature of an isotropic phase islowered and the viscosity is increased as shown in the following:

NI (° C.)¹⁾ η (mPa · s)²⁾

62.7 22.3

61.6 24.5

82.2 26.1

77.4 27.1

73.0 27.3 ¹⁾Measurement results after dissolving the compound in liquidcrystal composition ZLI-1132 manufactured by Merck Company.²⁾Measurement results at 20° C.

However, in the compounds of the present invention, these disadvantagesare not found, and there is the unexpected effect that a high transitiontemperature of an isotropic phase and low viscosity are maintained andthe compatibility is improved.

Since the compounds of the present invention have excellent stabilityand a high voltage holding ratio, in addition to a TN type and a STNtype, in a TFT type of liquid crystal compositions requiring the highvoltage holding ratio, the compounds can be preferably used as theingredients constituting the compositions.

In the compounds of the present invention, the compounds having 3 or 4cyclohexane rings in a molecule show very high transition temperature ofan isotropic phase and small Δ n and relatively low viscosity. On theother hand, the compounds having 3 or 4 aromatic rings show large Δ n,and the compounds having a pyrimidine ring, pyridine ring or dioxanering show relatively large Δε. Further, by substituting fluorine atomsfor hydrogen atoms, it is possible to improve Δε and the compatibility.

Since the compounds wherein R is an alkenyl group show a large elasticconstant ratio (bend elastic constant/splay elastic constant), and thechange of transmission is steep, the compounds are preferred in a STNtype of liquid crystal compositions.

Moreover, where X denotes F, Cl, Br, I or OH, F is specificallypreferred for imparting stability and viscosity.

As shown in the above, by selecting any six-membered rings, substitutinggroups and/or bonding groups, new liquid crystalline compounds havingdesired physical properties may be obtained.

The liquid crystal compositions provided by the present invention may bethe first constituent containing at least one kind of the liquidcrystalline compounds represented by the general formula (1), and inaddition, as the second constituent, a mixture of at least one kind ofthe compounds selected from the group of aforesaid general formulas (2),(3) and (4) (designated as the second 2A constituent) and/or at leastone kind of the compounds selected from the group of aforesaid generalformulas (5), (6), (7), (8) and (9) (designated as the second 2Bconstituent) is preferred. Further, to adjust a threshold voltage, atemperature range of the liquid crystal phase, the refractive indexanisotropy value, the dielectric anisotropy value, viscosity and thelike, known compounds may be mixed as the third constituent.

In the above-mentioned second 2A constituent, the following compounds(2-1)-(2-15) preferably contained in general formula (2), the followingcompounds (3-1)-(3-48) preferably contained in general formula (3), andthe following compounds (4-1)-(4-55) preferably contained in generalformula (4) can be exemplified, respectively.

(2-1)

(2-2)

(2-3)

(2-4)

(2-5)

(2-6)

(2-7)

(2-8)

(2-9)

(2-10)

(2-11)

(2-12)

(2-13)

(2-14)

(2-15)

(3-1)

(3-2)

(3-3)

(3-4)

(3-5)

(3-6)

(3-7)

(3-8)

(3-9)

(3-10)

(3-11)

(3-12)

(3-13)

(3-14)

(3-15)

(3-16)

(3-17)

(3-18)

(3-19)

(3-20)

(3-21)

(3-22)

(3-23)

(3-24)

(3-25)

(3-26)

(3-27)

(3-28)

(3-29)

(3-30)

(3-31)

(3-32)

(3-33)

(3-34)

(3-35)

(3-36)

(3-37)

(3-38)

(3-39)

(3-40)

(3-41)

(3-42)

(3-43)

(3-44)

(3-45)

(3-46)

(3-47)

(3-48)

(4-1)

(4-2)

(4-3)

(4-4)

(4-5)

(4-6)

(4-7)

(4-8)

(4-9)

(4-10)

(4-11)

(4-12)

(4-13)

(4-14)

(4-15)

(4-16)

(4-17)

(4-18)

(4-19)

(4-20)

(4-21)

(4-22)

(4-23)

(4-24)

(4-25)

(4-26)

(4-27)

(4-28)

(4-29)

(4-30)

(4-31)

(4-32)

(4-33)

(4-34)

(4-35)

(4-36)

(4-37)

(4-38)

(4-39)

(4-40)

(4-41)

(4-42)

(4-43)

(4-44)

(4-45)

(4-46)

(4-47)

(4-48)

(4-49)

(4-50)

(4-51)

(4-52)

(4-53)

(4-54)

(4-55)

These compounds represented by general formula (2)-(4) have positivedielectric anisotropy value and excellent thermostability and chemicalstability.

The usage of the compounds is suitably 1-99% by weight based on thetotal weight of the liquid crystal composition, preferably 10-97% byweight, and more preferably 40-95% by weight.

Moreover, in the above-mentioned second 2B constituents, as preferredcompounds contained in general formulas (5), (6) and (7), (5-1)-(5-24),(6-1)-(6-3) and (7-1)-(7-17) can be exemplified.

(5-1)

(5-2)

(5-3)

(5-4)

(5-5)

(5-6)

(5-7)

(5-8)

(5-9)

(5-10)

(5-11)

(5-12)

(5-13)

(5-14)

(5-15)

(5-16)

(5-17)

(5-18)

(5-19)

(5-20)

(5-21)

(5-22)

(5-23)

(5-24)

(6-1)

(6-2)

(6-3)

(7-1)

(7-2)

(7-3)

(7-4)

(7-5)

(7-6)

(7-7)

(7-8)

(7-9)

(7-10)

(7-11)

(7-12)

(7-13)

(7-14)

(7-15)

(7-16)

(7-17)

The compounds represented by general formulas (5)-(7) have a positiveand high dielectirc anisotropy value and can be particularly used as aconstituent of the composition to reduce the threshold voltage. Inaddition, these compounds are used to adjust the viscosity and therefractive index anisotropy value, to spread the region of temperatureof the liquid crystal phase and to improve the steepness properties.

In the second 2B constituent, (8-1)-(8-8) and (9-1)-(9-12) can beexemplified as preferred embodiments of the compounds contained ingeneral formulas (8) and (9), respectively.

(8-1)

(8-2)

(8-3)

(8-4)

(8-5)

(8-6)

(8-7)

(8-8)

(9-1)

(9-2)

(9-3)

(9-4)

(9-5)

(9-6)

(9-7)

(9-8)

(9-9)

(9-10)

(9-11)

(9-11)

(9-12)

These compounds represented by general formulas (8) and (9) have anegative or week positive dielectric anisotropy value. In thesecompounds, the compound represented by general formula (8) is used as aconstituent of the composition for lowering the viscosity and forregulation of the dielectric anisotropy value, and the compoundrepresented by general formula (9) is used for spreading the region oftemperature of the liquid crystal phase and/or for regulation of thedielectric anisotropy value.

The compounds represented by the above general formulas (5)-(9) arecompounds necessary to prepare liquid crystal compositions for a displaymode of a STN type or a common display mode of a TN type. In case ofpreparation of common display modes of the STN type or the TN type,suitable usage of the compound is 1-99% by weight based on the totalweight of the liquid crystal composition, preferably 10-97% by weight,and more preferably 40-95% by weight.

The liquid crystal composition provided by the present inventioncontains preferably 0.1-99% by weight of at least one kind of liquidcrystalline compounds represented by general formula (1) to develop goodcharacteristics.

The liquid crystal composition can be commonly prepared by methods, forexample by a method wherein many kinds of constituents are dissolved ineach other at a high temperature. If necessary, suitable additives areadded to improve and optimize according to the demand of desired use.Such additives are well-known by persons concerned in the field, anddescribed in detail in literature and the like. Usually, a chiral dopantand the like are added. The agent has properties that the helicalstructure of liquid crystals is induced to adjust a necessary twistedangle and prevented a reverse twist.

When dichroic dyes such as merocyanine series, styryl series, azoseries, azomethine series, azoxy series, quinophthalone series,anthraquinone series and tetrazine series are added, the composition canbe used as a liquid crystal composition for a GH mode. The compositionof the present invention can be used for NCAP, which is prepared bymicrocapsulation of a nematic liquid crystal, or the composition can beused for a device of polymer-dispersion type liquid crystal display(PDLCD) which is prepared by working three dimensional crosslinkedpolymer in liquid crystal, for example, a device of polymer networkliquid crystal display (PNLCD), further, for an electrically controlledbirefringence (ECB) mode and a DS mode.

The following show examples of liquid crystal compositions containingthe compounds of the present invention. The numbers of the compounds arethe same as the numbers represented in after-mentioned examples.

Composition example 1

(No. 3) 6 wt %

(No. 4) 6 wt %

(No. 5) 6 wt %

10 wt % 

10 wt % 

3 wt %

10 wt % 

10 wt % 

10 wt % 

3 wt %

2 wt %

3 wt %

4 wt %

4 wt %

4 wt %

6 wt %

3 wt %

Composition example 2

(No. 3) 6 wt %

(No. 4) 6 wt %

(No. 5) 4 wt %

8 wt %

8 wt %

14 wt % 

8 wt %

4 wt %

8 wt %

6 wt %

8 wt %

5 wt %

4 wt %

6 wt %

5 wt %

Composition example 3

(No. 1) 5 wt %

(No. 3) 5 wt %

(No. 4) 5 wt %

(No. 5) 5 wt %

13 wt % 

13 wt % 

8 wt %

8 wt %

8 wt %

6 wt %

10 wt % 

3 wt %

2 wt %

3 wt %

3 wt %

3 wt %

Composition example 4

(No. 1) 4 wt %

(No. 3) 5 wt %

(No. 4) 4 wt %

 (No. 38) 3 wt %

5 wt %

2 wt %

10 wt % 

10 wt % 

4 wt %

4 wt %

4 wt %

4 wt %

4 wt %

4 wt %

4 wt %

4 wt %

6 wt %

8 wt %

3 wt %

4 wt %

4 wt %

Composition example 5

(No. 1)  4 wt %

(No. 38) 4 wt %

(No. 40) 4 wt %

10 wt % 

10 wt % 

10 wt % 

8 wt %

10 wt % 

2 wt %

2 wt %

3 wt %

3 wt %

3 wt %

3 wt %

2 wt %

2 wt %

10 wt % 

4 wt %

2 wt %

2 wt %

2 wt %

Composition example 6

(No. 27)  4 wt %

(No. 28)  3 wt %

(No. 158) 4 wt %

(No. 159) 3 wt %

10 wt % 

10 wt % 

10 wt % 

6 wt %

6 wt %

8 wt %

6 wt %

6 wt %

5 wt %

4 wt %

6 wt %

3 wt %

3 wt %

3 wt %

Composition example 7

(No. 3) 5 wt %

(No. 4) 5 wt %

(No. 6) 3 wt %

(No. 7) 3 wt %

15 wt % 

12 wt % 

12 wt % 

5 wt %

4 wt %

2 wt %

2 wt %

2 wt %

10 wt % 

10 wt % 

10 wt% 

Composition example 8

(No. 120) 3 wt %

(No. 121) 5 wt %

(No. 142) 6 wt %

(No. 72)  6 wt %

(No. 75)  6 wt %

12 wt % 

10 wt % 

10 wt % 

6 wt %

6 wt %

6 wt %

4 wt %

3 wt %

2 wt %

4 wt %

4 wt %

3 wt %

2 wt %

2 wt %

Composition example 9

(No. 213) 3 wt %

(No. 214) 2 wt %

(No. 166) 4 wt %

(No. 168) 4 wt %

5 wt %

10 wt % 

5 wt %

15 wt % 

8 wt %

5 wt %

5 wt %

5 wt %

6 wt %

2 wt %

6 wt %

4 wt %

4 wt %

2 wt %

2 wt %

3 wt %

Composition example 10

(No. 174) 5 wt %

(NO. 176) 5 wt %

(No. 89)  5 wt %

18 wt % 

4 wt %

10 wt % 

4 wt %

4 wt %

8 wt %

6 wt %

2 wt %

10 wt % 

10 wt % 

4 wt %

5 wt %

Composition example 11

(No. 38) 5 wt %

(No. 40) 5 wt %

(No. 41) 4 wt %

10 wt % 

12 wt % 

12 wt % 

12 wt % 

8 wt %

4 wt %

8 wt %

5 wt %

5 wt %

10 wt % 

Composition example 12

(No. 38) 6 wt %

(No. 40) 6 wt %

(No. 41) 6 wt %

6 wt %

6 wt %

4 wt %

13 wt % 

13 wt % 

5 wt %

5 wt %

5 wt %

3 wt %

3 wt %

13 wt % 

6 wt %

Composition example 13

(No. 1)  5 wt %

(No. 3)  4 wt %

(No. 38) 5 wt %

(No. 41) 5 wt %

7 wt %

8 wt %

6 wt %

6 wt %

12 wt % 

5 wt %

8 wt %

5 wt %

8 wt %

10 wt % 

3 wt %

3 wt %

Composition example 14

(No. 87) 5 wt %

(No 88) 4 wt %

(No. 93) 5 wt %

(No. 94) 4 wt %

3 wt %

2 wt %

10 wt % 

10 wt % 

10 wt % 

5 wt %

5 wt %

10 wt % 

5 wt %

3 wt %

8 wt %

6 wt %

3 wt %

2 wt %

Composition example 15

(NO. 20)  5 wt %

(No. 152) 6 wt %

(No. 154) 4 wt %

(No. 155) 4 wt %

8 wt %

6 wt %

3 wt %

4 wt %

4 wt %

4 wt %

7 wt %

7 wt %

14 wt % 

5 wt %

4 wt %

4 wt %

4 wt %

3 wt %

2 wt %

2 wt %

Composition example 16

(No. 1) 3 wt %

(No. 3) 4 wt %

(No. 4) 4 wt %

(No. 5) 2 wt %

10 wt % 

10 wt % 

10 wt % 

10 wt % 

6 wt %

6 wt %

3 wt %

3 wt %

5 wt %

5 wt %

5 wt %

6 wt %

4 wt %

4 wt %

Composition example 17

(No. 208) 3 wt %

(No. 167) 3 wt %

(No. 182) 8 wt %

(No. 185) 8 wt %

(NO. 186) 6 wt %

10 wt % 

5 wt %

3 wt %

5 wt %

5 wt %

3 wt %

6 wt %

5 wt %

6 wt %

6 wt %

5 wt %

2 wt %

2 wt %

3 wt %

2 wt %

2 wt %

2 wt %

Composition example 18

(No. 99)  4 wt %

(No. 100) 4 wt %

(No. 109) 3 wt %

(No. 112) 4 wt %

11 wt % 

5 wt %

8 wt %

12 wt % 

5 wt %

3 wt %

3 wt %

5 wt %

5 wt %

5 wt %

5 wt %

4 wt %

5 wt %

6 wt %

3 wt %

Composition example 19

(No. 38) 5 wt %

(No. 40) 5 wt %

(No. 41) 5 wt %

12 wt % 

12 wt % 

12 wt % 

6 wt %

6 wt %

6 wt %

5 wt %

6 wt %

10 wt % 

10 wt % 

Composition example 20

(No. 183) 4 wt %

(No. 184) 4 wt %

(No. 124) 4 wt %

8 wt %

7 wt %

8 wt %

3 wt %

3 wt %

3 wt %

3 wt %

3 wt %

3 wt %

2 wt %

2 wt %

4 wt %

3 wt %

8 wt %

8 wt %

8 wt %

8 wt %

2 wt %

2 wt %

Composition example 21

(No. 14) 3 wt %

(No. 15) 3 wt %

(No. 17) 3 wt %

(No. 43) 3 wt %

10 wt % 

5 wt %

3 wt %

5 wt %

5 wt %

3 wt %

6 wt %

5 wt %

6 wt %

6 wt %

5 wt %

2 wt %

2 wt %

3 wt %

2 wt %

2 wt %

2 wt %

Composition example 22

(No. 82)  5 wt %

(No. 34)  4 wt %

(No. 62)  5 wt %

(No. 205) 4 wt %

3 wt %

2 wt %

10 wt % 

10 wt % 

10 wt % 

5 wt %

5 wt %

10 wt % 

5 wt %

3 wt %

8 wt %

6 wt %

3 wt %

2 wt %

Examples of compositions are further shown in the followings, Table 1shows compound symbols given as those in the columns “symbols”, whichare refered to their left columns, i.e. left end groups, bonding groups,ring structures, and right end groups.

TABLE 1 Symbols 1) Left end groups C_(n)H_(2n+1)— n- C_(n)H_(2n+1)O— nO-C_(n)H_(2n+1)OC_(m)H_(2m)— nOm- CH₂═CH— V- CH₂═CHC_(n)H_(2n)— Vn-C_(n)H_(2n+1)CH═CHC_(m)H_(2m)— nVm-C_(n)H_(2n+1)CH═CHC_(m)H_(2m)CH═CHC_(k)H_(2k)— nVmVk- 2) Ring Structure

B

B(F)

B(2F)

B(F,F)

H

Py

D

Ch 3) Bonding groups —C₂H₄— 2 —C₄H₈— 4 —COO— E —C≡C— T —CH═CH═ V —CF₂O—CF2O —OCF₂— OCF2 4) Right end groups —F —F —Cl —CL —CN —C —CF₃ —CF₃—OCF₃ —OCF₃ —OCF₂H —OCF2H —C_(n)H_(2n+1) -n —OC_(n)H_(2n+1) -On —COOCH₃-EMe —C_(n)H_(2n)CH═CH₂ -nV —C_(n)H_(2m)CH═CHC_(n)H_(2n+1) -mVn—C_(m)H_(2m)CH═CHC_(n)H_(2n)F -mVnF —CH═CF₂ -VFF —C_(n)H_(2n)F -nF

Composition example 23 4-HBBH-4F (No. 1) 5.0 wt % 1V2-BEB(F,F)-C 5.0 wt% 3-HB-C 25.0 wt % 1-BTB-3 5.0 wt % 2-BTB-1 10.0 wt % 3-HH-4 11.0 wt %3-HHB-1 11.0 wt % 3-HHB-3 5.0 wt % 3-H2BTB-2 3.0 wt % 3-H2BTB-3 4.0 wt %3-H2BTB-4 4.0 wt % 3-HB(F)TB-2 6.0 wt % 3-HB(F)TB-3 6.0 wt %

Composition example 24 4-HBBH-4F (No. 1) 5.0 wt % V2-HB-C 12.0 wt %1V2-HB-C 12.0 wt % 3-HB-C 24.0 wt % 3-HB(F)-C 5.0 wt % 2-BTB-1 2.0 wt %3-HH-4 8.0 wt % 3-HH-VFF 6.0 wt % 2-HHB-C 3.0 wt % 3-HHB-C 6.0 wt %3-HB(F)TB-2 8.0 wt % 3-H2BTB-2 3.0 wt % 3-H2BTB-3 3.0 wt % 3-H2BTB-4 3.0wt %

Composition example 25 4-HBBH-4F (No. 1) 3.0 wt % 5-HBBH-1F (No. 5) 3.0wt % 2O1-BEB(F)-C 5.0 wt % 3O1-BEB(F)-C 15.0 wt % 4O1-BEB(F)-C 13.0 wt %5O1-BEB(F)-C 13.0 wt % 2-HHB(F)-C 15.0 wt % 3-HHB(F)-C 15.0 wt %3-HB(F)TB-2 3.0 wt % 3-HB(F)TB-3 2.0 wt % 3-HB(F)TB-4 3.0 wt % 3-HHB-18.0 wt % 3-HHB-O1 2.0 wt %

Composition example 26 3-HBBH-3F (No. 7) 4.0 wt % 4-HBBH-4F (No. 1) 5.0wt % 5-PyB-F 4.0 wt % 3-PyB(F)-F 4.0 wt % 2-BB-C 5.0 wt % 4-BB-C 4.0 wt% 5-BB-C 5.0 wt % 2-PyB-2 2.0 wt % 3-PyB-2 2.0 wt % 4-PyB-2 2.0 wt %6-PyB-O5 3.0 wt % 6-PyB-O6 3.0 wt % 6-PyB-O7 3.0 wt % 6-PyB-O8 3.0 wt %3-PyBB-F 6.0 wt % 4-PyBB-F 6.0 wt % 5-PyBB-F 6.0 wt % 3-HHB-1 6.0 wt %3-HHB-3 4.0 wt % 2-H2BTB-2 4.0 wt % 2-H2BTB-3 4.0 wt % 2-H2BTB-4 5.0 wt% 3-H2BTB-3 5.0 wt % 3-H2BTB-4 5.0 wt %

Composition example 27 3-HBBH-5F (No. 10) 3.0 wt % 3-DB-C 10.0 wt %4-DB-C 10.0 wt % 2-BEB-C 12.0 wt % 3-BEB-C 4.0 wt % 3-PyB(F)-F 6.0 wt %3-HEB-O4 8.0 wt % 4-HEB-O2 6.0 wt % 5-HEB-O1 6.0 wt % 3-HEB-O2 5.0 wt %5-HEB-O2 4.0 wt % 5-HEB-5 5.0 wt % 4-HEB-5 5.0 wt % 1O-BEB-2 4.0 wt %3-HHB-1 3.0 wt % 3-HHEBB-C 3.0 wt % 3-HBEBB-C 3.0 wt % 5-HBEBB-C 3.0 wt%

Composition example 28 3O1-HBBH-2F (No. 14) 4.0 wt % 3-HB-C 18.0 wt %5-HB-C 3.0 wt % 1O1-HB-C 10.0 wt % 3-HB(F)-C 10.0 wt % 2-PyB-2 2.0 wt %3-PyB-2 2.0 wt % 4-PyB-2 2.0 wt % 1O1-HH-3 7.0 wt % 2-BTB-O1 7.0 wt %3-HHB-1 7.0 wt % 3-HHB-F 4.0 wt % 3-HHB-O1 4.0 wt % 3-HHB-3 4.0 wt %3-H2BTB-2 3.0 wt % 3-H2BTB-3 3.0 wt % 2-PyBH-3 4.0 wt % 3-PyBH-3 3.0 wt% 3-PyBB-2 3.0 wt %

Composition example 29 4-HBBH-4F (No. 1) 4.0 wt % 3-HBB(2F)H-5F (No. 46)3.0 wt % 2O1-BEB(F)-C 5.0 wt % 3O1-BEB(F)-C 12.0 wt % 5O1-BEB(F)-C 4.0wt % 1V2-BEB(F,F)-C 10.0 wt % 3-HH-EMe 10.0 wt % 3-HB-O2 18.0 wt %3-HHEB-F 3.0 wt % 5-HHEB-F 3.0 wt % 3-HBEB-F 4.0 wt % 2O1-HBEB(F)-C 2.0wt % 3-HB(F)EB(F)-C 2.0 wt % 3-HBEB(F,F)-C 2.0 wt % 3-HHB-F 4.0 wt %3-HHB-O1 4.0 wt % 3-HHB-3 6.0 wt % 3-HEBEB-F 2.0 wt % 3-HEBEB-1 2.0 wt %

Composition example 30 3-HBB(2F)H-3F (No. 45) 3.0 wt % 2O1-BEB(F)-C 5.0wt % 3O1-BEB(F)-C 12.0 wt % 5O1-BEB(F)-C 4.0 wt % 1V2-BEB(F,F)-C 16.0 wt% 3-HB-O2 10.0 wt % 3-HH-4 3.0 wt % 3-HHB-F 3.0 wt % 3-HHB-1 8.0 wt %3-HHB-O1 4.0 wt % 3-HBEB-F 4.0 wt % 3-HHEB-F 7.0 wt % 5-HHEB-F 7.0 wt %3-H2BTB-2 4.0 wt % 3-H2BTB-3 4.0 wt % 3-H2BTB-4 4.0 wt % 3-HB(F)TB-2 2.0wt %

Composition example 31 3-HBBH-5F (No. 10)  3.0 wt % 3-HBBH-3F (No. 7) 3.0 wt % 2-BEB-C 12.0 wt % 3-BEB-C  4.0 wt % 4-BEB-C  6.0 wt % 3-HB-C28.0 wt % 3-HEB-O4 12.0 wt % 4-HEB-O2  8.0 wt % 5-HEB-O1  8.0 wt %3-HEB-O2  6.0 wt % 5-HEB-O2  5.0 wt % 3-HHB-1  3.0 wt % 3-HHB-O1  2.0 wt%

Composition example 32 4-HBBH-4F (No. 1)  4.0 wt % 3-HBBH-3F (No. 7) 4.0 wt % 2-BEB-C 10.0 wt % 5-BB-C 12.0 wt % 7-BB-C  7.0 wt % 1-BTB-3 7.0 wt % 2-BTB-1 10.0 wt % 1O-BEB-2 10.0 wt % 1O-BEB-5 12.0 wt %2-HHB-1  4.0 wt % 3-HHB-F  4.0 wt % 3-HHB-1  7.0 wt % 3-HHB-O1  4.0 wt %3-HHB-3  5.0 wt %

Composition example 33 4-HBBH-4F (No. 1)  5.0 wt % 2-HHB(F)-F 15.0 wt %3-HHB(F)-F 15.0 wt % 5-HHB(F)-F 15.0 wt % 2-H2HB(F)-F 10.0 wt %3-H2HB(F)-F  5.0 wt % 5-H2HB(F)-F 10.0 wt % 2-HBB(F)-F  6.0 wt %3-HBB(F)-F  6.0 wt % 5-HBB(F)-F 13.0 wt %

Composition example 34 4-HBBH-4F (No. 1)  5.0 wt % 3-HBB(2F)H-3F (No.45)  3.0 wt % 7-HB(F)-F  5.0 wt % 5-H2B(F)-F  5.0 wt % 3-HH-4  5.0 wt %3-HB-O2 10.0 wt % 2-HHB(F)-F 10.0 wt % 3-HHB(F)-F 10.0 wt % 5-HHB(F)-F10.0 wt % 3-H2HB(F)-F  5.0 wt % 2-HBB(F)-F  3.0 wt % 3-HBB(F)-F  3.0 wt% 5-HBB(F)-F  6.0 wt % 2-H2BB(F)-F  5.0 wt % 3-H2BB(F)-F  6.0 wt %3-HHB-1  4.0 wt % 3-HHB-O1  3.0 wt % 3-HHB-3  2.0 wt %

Composition example 35 5-HBBH-1F (No. 5)  3.0 wt % 3-HBBH-5F (No. 10) 3.0 wt % 7-HB(F,F)-F  3.0 wt % 3-HB-O2  7.0 wt % 2-HHB(F)-F  8.0 wt %3-HHB(F)-F  8.0 wt % 5-HHB(F)-F  8.0 wt % 2-HBB(F)-F  9.0 wt %3-HBB(F)-F  9.0 wt % 5-HBB(F)-F 16.0 wt % 2-HBB-F  4.0 wt % 3-HBB-F  4.0wt % 5-HBB-F  3.0 wt % 3-HBB(F,F)-F  5.0 wt % 5-HBB(F,F)-F 10.0 wt %

Composition example 36 3-HBB(2F)H-3F (No. 45)  3.0 wt % 3-HBB(2F)H-5F(No. 46)  3.0 wt % 7-HB(F,F)-F  4.0 wt % 3-H2HB(F,F)-F 12.0 wt %4-H2HB(F,F)-F 10.0 wt % 5-H2HB(F,F)-F 10.0 wt % 3-HHB(F,F)-F 10.0 wt %4-HHB(F,F)-F  5.0 wt % 3-HH2B(F,F)-F 12.0 wt % 5-HH2B(F,F)-F  7.0 wt %3-HBB(F,F)-F 12.0 wt % 5-HBB(F,F)-F 12.0 wt %

Composition example 37 3-HBBH-3F (No. 7)  4.0 wt % 3-HB-CL 10.0 wt %5-HB-CL  4.0 wt % 7-HB-CL  4.0 wt % 1O1-HH-5  5.0 wt % 2-HBB(F)-F  8.0wt % 3-HBB(F)-F  8.0 wt % 5-HBB(F)-F 14.0 wt % 4-HHB-CL  8.0 wt %5-HHB-CL  8.0 wt % 3-H2HB(F)-CL  4.0 wt % 3-HBB(F,F)-F 10.0 wt %5-H2BB(F,F)-F  9.0 wt % 3-HB(F)VB-2  2.0 wt % 3-HB(F)VB-3  2.0 wt %

Composition example 38 4-HBBH-4F (No. 1)  2.0 wt % 3O1-HBBH-2F (No. 14) 4.0 wt % 3-HHB(F,F)-F  9.0 wt % 3-H2HB(F,F)-F  8.0 wt % 4-H2HB(F,F)-F 8.0 wt % 5-H2HB(F,F)-F  8.0 wt % 3-HBB(F,F)-F 21.0 wt % 5-HBB(F,F)-F20.0 wt % 3-H2BB(F,F)-F 10.0 wt % 5-HHBB(F,F)-F  2.0 wt % 3-HH2BB(F,F)-F 2.0. wt % 5-HHEBB-F  2.0 wt % 1O1-HBBH-4  2.0 wt % 1O1-HBBH-5  2.0 wt %

Composition example 39 4-HBBH-4F (No. 1)  2.0 wt % 3-HBB(2F)H-5F (No.46)  2.0 wt % 5-HB-F 12.0 wt % 6-HB-F  9.0 wt % 7-HB-F  7.0 wt %2-HHB-OCF3  7.0 wt % 3-HHB-OCF3  9.0 wt % 4-HHB-OCF3  7.0 wt %5-HHB-OCF3  5.0 wt % 3-HH2B-OCF3  4.0 wt % 5-HH2B-OCF3  4.0 wt %3-HHB(F,F)-OCF3  5.0 wt % 3-HBB(F)-F 10.0 wt % 5-HBB(F)-F 10.0 wt %3-HH2B(F)-F  3.0 wt % 3-HB(F)BH-3  2.0 wt % 5-HBBH-3  2.0 wt %

Composition example 40 4-HBBH-4F (No. 1)  3.0 wt % 3-HBB(2F)H-3F (No.45)  4.0 wt % 5-H4HB(F,F)-F  7.0 wt % 5-H4HB-OCF3  8.0 wt %3-H4HB(F,F)-CF3  8.0 wt % 5-H4HB(F,F)-CF3 10.0 wt % 3-HB-CL  6.0 wt %5-HB-CL  4.0 wt % 2-H2BB(F)-F  5.0 wt % 3-H2BB(F)-F 10.0 wt %5-HVHB(F,F)-F  5.0 wt % 3-HHB-OCF3  5.0 wt % 3-H2HB-OCF3  5.0 wt %V-HHB(F)-F  5.0 wt % 3-HChB(F)-F  5.0 wt % 5-HHEB-OCF3  2.0 wt %3-HBEB(F,F)-F  5.0 wt % 5-HH-V2F  3.0 wt %

Composition example 41 4-HBBH-4F (No. 1)  5.0 wt % 2-HHB(F)-F  2.0 wt %3-HHB(F)-F  2.0 wt % 5-HHB(F)-F  2.0 wt % 2-HBB(F)-F  6.0 wt %3-HBB(F)-F  6.0 wt % 5-HBB(F)-F 10.0 wt % 2-H2BB(F)-F  9.0 wt %3-H2BB(F)-F  9.0 wt % 3-HBB(F,F)-F 25.0 wt % 5-HBB(F,F)-F 19.0 wt %1O1-HBBH-4  3.0 wt % 1O1-HBBH-5  2.0 wt %

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a graph illustrating the effect of liquid crystalcomposition examples of the present invention in relation to a voltageholding ratio (%) and T (° C.). (a) shows a mother liquid crystalcomposition, (b) shows an example of a liquid crystal composition of thepresent invention, (c) shows a comparative example of a liquid crystalcomposition and (d) shows another comparative example of a liquidcrystal composition.

BEST MODE FOR CARRYING OUT THE INVENTION

The following examples illustrate the present invention morespecifically. In each example, C shows a crystal, SA shows a smectic Aphase, SB shows a smectic B phase, Sx shows a smectic phase in which thephase structure is not analyzed, N shows a nematic phase and I shows anisotropic phase, and the unit of phase transition temperature is 20 C.

EXAMPLE 1

Preparation of4-(trans-4-(4-fluorobutyl)cyclohexyl)-4′-(trans-4-butylcyclohexyl)biphenyl(in general formula (1), wherein R is C₄H₉, m is 4, X is F, both A₁ andA₄ are trans-1,4-cyclohexylene groups, both A₂ and A₃ are 1,4-phenylenegroups, all of Z₁, Z₂, and Z₃ are covalent bonds) (Compound No. 1)

4-(Trans-4-(4-Hydroxybutyl)cyclohexyl)-4′-(trans-4-butylcyclohexyl)biphenyl 6.3 g (0.014 mol) anddichloromethane 50 ml were mixed. To the mixture, a solution of DAST 3.4g (0.021 mol) in dichloromethane 7 ml were added dropwise to maintainthe temperature at −50° C., and the mixture was stirred for 30 minutesat the same temperature. Then, the temperature was increased slowly andthe mixture was stirred for 6 hours at room temperature.

The reaction mixture was poured into ice water 100 ml and extracted withdichloromethane 100 ml. The obtained organic phase was washed with waterthree times and dried over anhydrous magnesium sulfate. The solvent wasdistilled out under reduced pressure, the residue was chromatographedover silica gel (elute: toluene/heptane) to obtain 5.0 g of crude4-(trans-4-(4-fluorobutyl)cyclohexyl)-4′-(trans-4-butylcyclohexyl)biphenyl.The resulting compound was recrystallized from ethyl acetate, and 20 gof the title compound (yield: 42.9%) was obtained.

C 64 Sx 235 N 298 I

Moreover, the structure was supported by each spectrum data.

Mass spectrometric analysis: 448 (M⁺)

¹H-NMR (CDCl₃, TMS internal standard)

δ (ppm)

0.81-2.61 (m, 35H)

4.45 (dt, 2H)

7.37 (dd, 8H)

The following compounds are prepared according to the above method ofExample 1 (No.2-No.34).

No.

24-(trans-4-fluoromethylcyclohexyl)-4′-(trans-4-ethylcyclohexyl)biphenyl

34-(trans-4-fluoromethylcyclohexyl)-4′-(trans-4-propylcyclohexyl)biphenyl

44-(trans-4-fluoromethylcyclohexyl)-4′-(trans-4-butylcyclohexyl)biphenyl

54-(trans-4-fluoromethylcyclohexyl)-4′-(trans-4-pentylcyclohexyl)biphenyl

C-Sx 103

N-I 292

64-(trans-4-(2-fluoroethyl)cyclohexyl)-4′-(trans-4-propylcyclohexyl)biphenyl

74-(trans-4-(3-fluoropropyl)cyclohexyl)-4′-(trans-4-propylcyclohexyl)biphenyl

84-(trans-4-(3-fluoropropyl)cyclohexyl)-4′-(trans-4-pentylcyclohexyl)biphenyl

C 61 Sx 236 N 314 I

94-(trans-4-(3-fluoropropyl)cyclohexyl)-4′-(trans-4-nonylcyclohexyl)biphenyl

10 4-(trans-4-(5-fluoropentyl)cyclohexyl)-4′-(trans-4-propylcyclohexyl)biphenyl

C-Sx 52

N-I 303

114-(trans-4-(8-fluorooctyl)cyclohexyl)-4′-(trans-4-ethylcyclohexyl)biphenyl

12 4-(trans-4-(8-fluorooctyl)cyclohexyl)-4′-(trans-4-heptylcyclohexyl)biphenyl

134-(trans-4-(4-fluorobutyl)cyclohexyl)-4′-(trans-4-ethoxycyclohexyl)biphenyl

144-(trans-4-(2-fluoroethyl)cyclohexyl)-4′-(trans-4-propoxymethylcyclohexyl)biphenyl

N-I 292

154-(trans-4-(5-fluoropentyl)cyclohexyl)-4′-(trans-4-ethenylcyclohexyl)biphenyl

16(E)-4-(trans-4-(3-fluoropropyl)cyclohexyl)-4′-(trans-4-(1-propenyl)cyclohexyl)biphenyl

17(E)-4-(trans-4-(2-fluoroethyl)cyclohexyl)-4′-(trans-4-(3-butenyl)cyclohexyl)biphenyl

184-(trans-4-(4-fluorobutyl)cyclohexyl)-4′-(trans-4-(2-propenyloxymethyl)cyclohexyl)biphenyl

194-(trans-4-(5-bromopentyl)cyclohexyl)-4′-(trans-4-propylcyclohexyl)biphenyl

204-(trans-4-(4-fluorobutyl)cyclohexyl)-4′-(2-(trans-4-propylcyclohexyl)ethyl)biphenyl

214-(trans-4-(2-fluoroethyl)cyclohexyl)-4′-(2-(trans-4-pentylcyclohexyl)ethyl)biphenyl

224-(trans-4-(5-fluoropentyl)cyclohexyl)-4′-(2-(trans-4-methoxypropylcyclohexyl)ethyl)biphenyl

234-(2-(trans-4-fluoromethylcyclohexyl)ethyl)-4′-(trans-4-pentylcyclohexyl)biphenyl

244-(2-(trans-4-(7-fluoroheptyl)cyclohexyl)ethyl)-4′-(trans-4-ethylcyclohexyl)biphenyl

25(E)-4-(2-(trans-4-(3-fluoropropyl)cyclohexyl)ethyl)-4′-(trans-4-(1-butenyl)cyclohexyl)biphenyl

264-(2-(trans-4-(5-fluoropentyl)cyclohexyl)ethyl)-4′-(trans-4-(2-propenyl)cyclohexyl)biphenyl

274-(2-(trans-4-chloromethylcyclohexyl)ethyl)-4′-(trans-4-propylcyclohexyl)biphenyl

284-(2-(trans-4-chloromethylcyclohexyl)ethyl)-4′-(trans-4-butylcyclohexyl)biphenyl

29 4-(3-fluoropropyl)-4′″-ethyl-1,1′:4′,1″:4″,1′″-quaterphenyl

30 4-(trans-4-(4-(4-fluorobutyl)phenyl)cyclohexyl)-4′-pentylbiphenyl

31(2-fluoroethyl)-4-(trans-4-(trans-4-(4-methylphenyl)cyclohexyl)cyclohexyl)benzene

32(trans-4-fluoromethylcyclohexyl)-4-(trans-4-(butylphenyl)cyclohexyl)benzene

33(trans-4-(3-fluoropropyl)cyclohexyl)-4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)benzene

34 4-(5-fluoropentyl)-4′″-pentyl-1,1′:4′,1″:4″,1′″-quatercyclohexane

EXAMPLE 2

Preparation of4-(trans-4-(3-fluoropropyl)cyclohexyl)-2′-fluoro-4′-(trans-4-pentylcyclohexyl)biphenyl(in general formula (1), R is C₅H₁₁, m is 3, X is F, both A₁ and A₄ aretrans-1,4-cyclohexylene groups, A₂ is a 2-fluoro-1,4-phenylene group, A₃is a 1,4-phenylene group, all of Z₁, Z₂, and Z₃ are covalent bonds)(No.35)

4-(trans-4-(3-hydroxypropyl)cyclohexyl)-2′-fluoro-4′-(trans-4-pentylcyclohexyl)biphenyl3.2 g (0.007 mol) and dichloromethane 30 ml were mixed. To the mixture,a solution of DAST 1.7 g (0.011 mol) in dichloromethane 4 ml were addeddropwise to maintain the temperature at −50 ° C., and stirred for 30minutes at the same temperature. Then, the temperature was increasedslowly and the mixture was stirred for 5 hours at room temperature.

The reaction mixture was poured into ice water 50 ml and extracted withdichloromethane 60 ml. The obtained organic phase was washed with waterthree times and dried over anhydrous magnesium sulfate. The solvent wasdistilled out under reduced pressure, the residue was chromatographedover silica gel (elate: toluene/heptane) to obtain 2.7 g of crude4-(trans-4-(3-fluoropropyl)cyclohexyl)-2′-fluoro-4′-(trans-4-pentylcyclohexyl)biphenyl.The resulting compound was recrystallized from ethyl acetate, and thetitle compound 1.4 g (yield: 43.6%) was obtained.

Moreover, the structure was supported by each spectrum data.

Mass spectrometric analysis: 466 (M⁺)

¹H-NMR (CDCl₃, TMS internal standard)

δ (ppm)

0.84-2.62 (m, 35H)

4.45 (dt, 2H)

7.33 (m, 7H)

The following compounds are prepared according to the above method ofExample 2 (No.36-No.68).

No.

36 4-(trans-4-(4-fluorobutyl)cyclohexyl)-2′-fluoro-4′-(trans-4-methylcyclohexyl)biphenyl

374-(trans-4-(5-fluoropentyl)cyclohexyl)-2′-fluoro-4′-(trans-4-ethylcyclohexyl)biphenyl

384-(trans-4-fluoromethylcyclohexyl)-2′-fluoro-4′-(trans-4-propylcyclohexyl)biphenyl

394-(trans-4-(4-fluorobutyl)cyclohexyl)-2′-fluoro-4′-(trans-4-butylcyclohexyl)biphenyl

404-(trans-4-fluoromethylcyclohexyl)-2′-fluoro-4′-(trans-4-butylcyclohexyl)biphenyl

414-(trans-4-fluoromethylcyclohexyl)-2′-fluoro-4′-(trans-4-pentylcyclohexyl)biphenyl

424-(trans-4-(3-bromopropyl)cyclohexyl)-2′-fluoro-4′-(trans-4-propylcyclohexyl)biphenyl

43 4- (trans-4-(4-fluorobutyl)cyclohexyl)-2′-fluoro-4′-(trans-4-ethenylcyclohexyl)biphenyl

442-fluoro-4-(trans-4-(2-fluoroethyl)cyclohexyl)-4′-(trans-4-ethylcyclohexyl)biphenyl

452-fluoro-4-(trans-4-(3-fluoropropyl)cyclohexyl-4′-(trans-4-propylcyclohexyl)biphenyl

C 43 Sx 124 N 302 I

462-fluoro-4-(trans-4-(5-fluoropentyl)cyclohexyl)-4′-(trans-4-propylcyclohexyl)biphenyl

C 79 Sx 118 N 294 I

472-fluoro-4-(trans-4-(6-fluorohexyl)cyclohexyl)-4′-(trans-4-pentylcyclohexyl)biphenyl

482-fluoro-4-(trans-4-(7-fluoroheptyl)cyclohexyl)-4′-(trans-4-octylcyclohexyl)biphenyl

492-fluoro-4-(trans-4-(3-fluoropropyl)cyclohexyl)-4′-(trans-4-butylcyclohexyl)biphenyl

502-fluoro-4-(trans-4-(5-fluoropentyl)cyclohexyl)-4′-(trans-4-methoxymethylcyclohexyl)biphenyl

514-(trans-4-fluoromethylcyclohexyl)-3′-fluoro-4′-(trans-4-propylcyclohexyl)biphenyl

52 4-(trans-4-(3-fluoropropyl)cyclohexyl)-3′-fluoro-4′-(trans-4-propylcyclohexyl)biphenyl

534-(trans-4-(6-fluorohexyl)cyclohexyl)-3′-fluoro-4′-(trans-4-butylcyclohexyl)biphenyl

544-(trans-4-(4-fluorobutyl)cyclohexyl)-3′-fluoro-4′-(trans-4-butylcyclohexyl)biphenyl

553-fluoro-4-(trans-4-(3-fluoropropyl)cyclohexyl)-4′-(trans-4-ethylcyclohexyl)biphenyl

563-fluoro-4-(trans-4-(4-fluorobutyl)cyclohexyl)-4′-(trans-4-butylcyclohexyl)biphenyl

57(E)-3-fluoro-4-(trans-4-(2-fluoroethyl)cyclohexyl)-4′-(trans-4-(1-pentenyl)cyclohexyl)biphenyl

584-(trans-4-(5-fluoropentyl)cyclohexyl)-2′,6′-difluoro-4′-(trans-4-methylcyclohexyl)biphenyl

594-(trans-4-(3-fluoropropyl)cyclohexyl)-2′,5′-difluoro-4′-(trans-4-propylcyclohexyl)biphenyl

602,3-difluoro-4-(trans-4-(2-fluoroethyl)cyclohexyl)-4′-(trans-4-ethylcyclohexyl)biphenyl

61 3,5-difluoro-4-(trans-4-(5-fluoropentyl)cyclohexyl)-4′-(trans-4-butylcyclohexyl)biphenyl

622-fluoro-4-(trans-4-(3-fluoropropyl)cyclohexyl)-2′-fluoro-4′-(trans-4-ethylcyclohexyl)biphenyl

63 2-fluoro-4-(trans-4-(3-fluoropropyl)cyclohexyl)-2′-fluoro-4′-(trans-4-propylcyclohexyl)biphenyl

64 2-fluoro-4-(trans-4-(2-fluoroethyl)cyclohexyl) -2′-fluoro-4′-(trans-4-butylcyclohexyl)biphenyl

652-fluoro-4-(trans-4-(5-fluoropentyl)cyclohexyl)-2′-fluoro-4′-(trans-4-pentylcyclohexyl)biphenyl

663-fluoro-4-(trans-4-(10-fluorodecyl)cyclohexyl)-2′-fluoro-4′-(trans-4-methylcyclohexyl)biphenyl

674-(trans-4-(7-fluoroheptyl)cyclohexyl)-3′-fluoro-4′-(2-(trans-4-ethylcyclohexyl)ethyl)biphenyl

68 2-fluoro-4-(2-(trans-4-(3-fluoropropyl)cyclohexyl)ethyl)-4′-(trans-4-pentylcyclohexyl)biphenyl

EXAMPLE 3

Preparation of4-(5-fluoropentyl)-4′-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)biphenyl(in general formula (1), R is C₃H₇, m is 5, X is F, both A₁ and A₂ aretrans-1,4-cyclohexylene groups, both A₃ and A₄ are 1,4-phenylene groups,and all of Z₁, Z₂, and Z₃ are covalent bonds)(No. 69)

4-(5-Hydroxypentyl)-4′-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)biphenyl5.2 g (0.012 mol) and dichloromethane 45 ml were mixed. To the mixture,a solution of DAST 2.8 g (0.018 mol) in dichloromethane 6 ml were addeddropwise to maintain the temperature at −50° C., and stirred for 30minutes at the same temperature. Then, the temperature was increasedslowly and the mixture was stirred for 6 hours at room temperature.

The reaction mixture was poured into ice water 100 ml and extracted withdichloromethane 100 ml.

The obtained organic phase was washed with water three times and driedover anhydrous magnesium sulfate. The solvent was distilled out underreduced pressure, the residue was chromatographed over silica gel(elute: toluene/heptane) to obtain 4.9 g of crude4-(5-fluoropentyl)-4′-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)biphenyl.The resulting compound was recrystallized from ethyl acetate, and 2.0 gthe title compound (yield: 38.5%) was obtained.

Moreover, the structure was supported by each spectrum data. Massspectrometric analysis: 448 (M⁺)

¹H-NMR (CDCl₃, TMS internal standard)

δ (ppm)

0.90-2.63 (m, 35H)

4.44 (dt, 2H)

7.38 (dd, 8H)

The following compounds are prepared according to the above method ofExample 3 (No.70-No.107).

No.

704-(2-fluoroethyl)-4′-(trans-4-(trans-4-methylcyclohexyl)cyclohexyl)biphenyl

714-(3-fluoropropyl)-4′-(trans-4-(trans-4-ethylcyclohexyl)cyclohexyl)biphenyl

724-(4-fluorobutyl)-4′-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)biphenyl

734-(5-fluoropentyl)-4′-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)biphenyl

744-(7-fluoroheptyl)-4′-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)biphenyl

754-(4-fluorobutyl)-4′-(trans-4-(trans-4-butylcyclohexyl)cyclohexyl)biphenyl

764-(3-fluoropropyl)-4′-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)biphenyl

77(E)-4-(2-fluoroethyl)-4′-(trans-4-(trans-4-(3-pentenyl)cyclohexyl)cyclohexyl)biphenyl

78(Z)-4-(4-fluorobutyl)-4′-(trans-4-(trans-4-(4-hexenyl)cyclohexyl)cyclohexyl)biphenyl

794-(3-bromopropyl)-4′-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)biphenyl

804-chloromethyl-4′-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)biphenyl

814-(trans-4-(trans-4-(3-fluoropropyl)cyclohexyl)cyclohexyl)-4′-methylbiphenyl

824-(trans-4-(trans-4-(2-fluoroethyl)cyclohexyl)cyclohexyl)-4′-propylbiphenyl

834-(trans-4-(trans-4-fluoromethylcyclohexyl)cyclohexyl)-4′-butylbiphenyl

844-(trans-4-(trans-4-(5-fluoropentyl)cyclohexyl)cyclohexyl)-4′-pentylbiphenyl

854-(trans-4-(trans-4-(6-fluorohexyl)cyclohexyl)cyclohexyl)-4′-methoxybiphenyl

864-(3-fluoropropyl)-4′-(trans-4-(2-(trans-4-ethylcyclohexyl)ethyl)cyclohexyl)biphenyl

874-(4-fluorobutyl)-4′-(trans-4-(2-(trans-4-propylcyclohexyl)ethyl)cyclohexyl)biphenyl

884-(4-fluorobutyl)-4′-(trans-4-(2-(trans-4-pentylcyclohexyl)ethyl)cyclohexyl)biphenyl

894-fluoromethyl-4′-(trans-4-(2-(trans-4-propylcyclohexyl)ethyl)cyclohexyl)biphenyl

904-(trans-4-(2-(trans-4-(3-fluoropropyl)cyclohexyl)ethyl)cyclohexyl)-4′-ethylbiphenyl

914-(trans-4-(2-(trans-4-(5-fluoropentyl)cyclohexyl)ethyl)cyclohexyl)-4′-pentylbiphenyl

924-(2-(4-(trans-4-(trans-4-methylcyclohexyl)cyclohexyl)phenyl)ethyl)-(4-fluorobutyl)benzene

934-(2-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)phenyl)ethyl)-fluoromethylbenzene

94 4-(2-(4-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)phenyl)ethyl)-fluoromethylbenzene

954-(2-(4-(trans-4-(trans-4-(3-butenyl)cyclohexyl)cyclohexyl)phenyl)ethyl)fluoromethylbenzene

964-hexyl-(2-(4-(trans-4-(trans-4-(2-fluoroethyl)cyclohexyl)cyclohexyl)phenyl)ethyl)benzene

974-ethoxyethyl-(2-(4-(trans-4-(trans-4-(4-fluorobutyl)cyclohexyl)cyclohexyl)phenyl)ethyl)benzene

983-fluoro-4-(7-fluoroheptyl)-4′-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)biphenyl

994-(4-fluorobutyl)-2′-fluoro-4′-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)biphenyl

1004-(4-fluorobutyl)-2′-fluoro-4′-(trans-4-(trans-4-butylcyclohexyl)cyclohexyl)biphenyl

1013-fluoro-4-(trans-4-(trans-4-(5-fluoropentyl)cyclohexyl)cyclohexyl)-4′-ethylbiphenyl

1024-(7-fluoroheptyl)-2′-fluoro-4′-(trans-4-(2-(trans-4-methylcyclohexyl)ethyl)cyclohexyl)biphenyl

1033,5-difluoro-4-(4-fluorobutyl)-4′-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)biphenyl

1043-fluoro-4-fluoromethyl-2′-fluoro-4′-(trans-4-(2-(trans-4-nonylcyclohexyl)ethyl)cyclohexyl)biphenyl

1053-fluoro-4-(trans-4-(2-(trans-4-fluoromethylcyclohexyl)ethyl)cyclohexyl)-4′-methylbiphenyl

1064-(2-(2-fluoro-4-(trans-4-(trans-4-ethenylcyclohexyl)cyclohexyl)phenyl)ethyl)-fluoromethylbenzene

1072-fluoro-4-butyl-(2-(2-fluoro-4-(trans-4-(trans-4-(2-fluoroethyl)cyclohexyl)cyclohexyl)phenyl)ethyl)benzene

EXAMPLE 4

Preparation of4-(3-fluoropropyl)-4′-(2-(trans-4-(trans-4-methylcyclohexyl)cyclohexyl)ethyl)biphenyl(in general formula (1), R is CH₃, m is 3, X is F, both A₁ and A₂ aretrans-1,4-cyclohexylene groups, both A₃ and A₄ are 1,4-phenylene groups,both Z₁ and Z₃ are covalent bonds, Z₂ is —(CH₂)₂—)(No. 108)4-(3-Hydroxypropyl)-4′-(2-(trans-4-(trans-4-methylcyclohexyl)cyclohexyl)ethyl)biphenyl5.9 g (0.014 mol) and dichloromethane 60 ml were mixed. To the mixture,a solution of DAST 3.4 g (0.021 mol) in dichloromethane 7 ml were addeddropwise to maintain the temperature at −50° C., and stirred for 30minutes at the same temperature. Then, the temperature was increasedslowly and the mixture was stirred for 7 hours at room temperature.

The reaction mixture was poured into ice water 150 ml and extracted withdichloromethane 120 ml.

The obtained organic phase was washed with water three times and driedover anhydrous magnesium sulfate. The solvent was distilled out underreduced pressure, the residue was chromatographed over silica gel(elute: toluene/heptane) to obtain 5.0 g of crude4-(3-fluoropropyl)-4′-(2-(trans-4-(trans-4-methylcyclohexyl)cyclohexyl)ethyl)biphenyl.The resulting compound was recrystallized from ethyl acetate, and 3.2 gof the title compound (yield: 54.2%) was obtained.

Moreover, the structure was supported by each spectrum data.

Mass spectrometric analysis: 420 (M⁺)

¹H-NMR (CDCl₃, TMS internal standard)

δ (ppm)

0.65-2.75 (m, 31H)

4.43 (dt, 2H)

7.38 (dd, 8H)

The following compounds are prepared according to the above method ofExample 4 (No.109-No.148).

No.

1094-fluoromethyl-4′-(2-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)ethyl)biphenyl

1104-(3-fluoropropyl)-4′-(2-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)ethyl)biphenyl

1114-(5-fluoropentyl)-4′-(2-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)ethyl)biphenyl

1124-fluoromethyl-4′-(2-(trans-4-(trans-4-butylcyclohexyl)cyclohexyl)ethyl)biphenyl

1134-(2-fluoroethyl)-4′-(2-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)ethyl)biphenyl

114 4-(8-fluorooctyl)-4′-(2-(trans-4-(trans-4-decylcyclohexyl)cyclohexyl)ethyl)biphenyl

115(E)-4-(2-fluoroethyl)-4′-(2-(trans-4-(trans-4-(1-propenyl)cyclohexyl)cyclohexyl)ethyl)biphenyl

116(Z)-4-(4-fluorobutyl)-4′-(2-(trans-4-(trans-4-(2-butenyl)cyclohexyl)cyclohexyl)ethyl)biphenyl

117(E)-4-fluoromethyl-4′-(2-(trans-4-(trans-4-(3-pentenyl)cyclohexyl)cyclohexyl)ethyl)biphenyl

1184-(6-fluorohexyl)-4′-(2-(trans-4-(trans-4-methoxycyclohexyl)cyclohexyl)ethyl)biphenyl

1194-(2-fluoroethyl)-4′-(2-(trans-4-(trans-4-methoxypropylcyclohexyl)cyclohexyl)ethyl)biphenyl

1204-chloromethyl-4′-(2-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)ethyl)biphenyl

1214-(2-chloroethyl)-4′-(2-(trans-4-(trans-4-butylcyclohexyl)cyclohexyl)ethyl)biphenyl

122 4-(3-iodopropyl)-4′-(2-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)ethyl)biphenyl

1234-(2-(trans-4-(trans-4-(2-fluoroethyl)cyclohexyl)cyclohexyl)ethyl)-4′-ethylbiphenyl

1244-(2-(trans-4-(trans-4-(4-fluorobutyl)cyclohexyl)cyclohexyl)ethyl)-4′-propylbiphenyl

1254-(2-(trans-4-(trans-4-(4-fluorobutyl)cyclohexyl)cyclohexyl)ethyl)-4′-butylbiphenyl

1264-(2-(trans-4-(trans-4-(3-fluoropropyl)cyclohexyl)cyclohexyl)ethyl)-4′-pentylbiphenyl

1274-(2-(trans-4-(trans-4-(5-fluoropentyl)cyclohexyl)cyclohexyl)ethyl)-4′-methylbiphenyl

1284-(2-(trans-4-(trans-4-(3-fluoropropyl)cyclohexyl)cyclohexyl)ethyl)-4′-pentyloxybiphenyl

1294-(2-(trans-4-(trans-4-(3-fluoropropyl)cyclohexyl)cyclohexyl)ethyl)-4′-ethoxymethylbiphenyl

1304-(2-(trans-4-(trans-4-(5-fluoropentyl)cyclohexyl)cyclohexyl)ethyl)-4′-methoxyethylbiphenyl

131 4-(2-(4-(trans-4-methylcyclohexyl)phenyl)ethyl)-(trans-4-(3-fluoropropyl)cyclohexyl)benzene

1324-(2-(4-(trans-4-propylcyclohexyl)phenyl)ethyl)-(trans-4-(2-fluoroethyl)cyclohexyl)benzene

1334-(2-(4-(trans-4-butylcyclohexyl)phenyl)ethyl)-(trans-4-(5-fluoropentyl)cyclohexyl)benzene

1344-(2-(4-(trans-4-hexylcyclohexyl)phenyl)ethyl)-(trans-4-(4-fluorobutyl)cyclohexyl)benzene

1354-(2-(4-(trans-4-ethenylcyclohexyl)phenyl)ethyl)-(trans-4-(3-fluoropropyl)cyclohexyl)benzene

1364-(2-(4-(trans-4-(3-butenyl)cyclohexyl)phenyl)ethyl)-(trans-4-(2-fluoroethyl)cyclohexyl)benzene

1374-(2-(4-(trans-4-metoxyethylcyclohexyl)phenyl)ethyl)-(trans-4-(5-fluoropentyl)cyclohexyl)benzene

138 4- (2-(4-(trans-4-propoxycyclohexyl)phenyl)ethyl)-(trans-4-(3-fluoropropyl)cyclohexyl)benzene

1394-(2-fluoroethyl)-3′-fluoro-4′-(2-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)ethyl)biphenyl

1403-fluoro-4-(3-fluoropropyl)-4′-(2-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)ethyl)biphenyl

1412-fluoro-4-(5-fluoropentyl)-2′-fluoro-4′-(2-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)ethyl)biphenyl

1424-chloromethyl-2′-fluoro-4′-(2-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)ethyl)biphenyl

143 2-fluoro-4-(2- (trans-4-(trans-4-(4-fluorobutyl)cyclohexyl)cyclohexyl)ethyl)-4′-methylbiphenyl

1443-fluoro-4-(2-(trans-4-(trans-4-(7-fluoroheptyl)cyclohexyl)cyclohexyl)ethyl)-4′-ethylbiphenyl

1453-fluoro-4-(2-(trans-4-(trans-4-(3-fluoropropyl)cyclohexyl)cyclohexyl)ethyl)-2′-fluoro-4′-butoxybiphenyl

1464-(2-(2-fluoro-4-(trans-4-pentylcyclohexyl)phenyl)ethyl)-(trans-4-fluoromethylcyclohexyl)benzene

1472-fluoro-4-(2-(2-fluoro-4-(trans-4-propylcyclohexyl)phenyl)ethyl)-(trans-4-(3-fluoropropyl)cyclohexyl)benzene

1483-fluoro-4-(2-(2-fluoro-4-(trans-4-propylcyclohexyl)phenyl)ethyl)-(trans-4-(5-fluoropentyl)cyclohexyl)benzene

EXAMPLE 5

Preparation of4-(trans-4-(2-(trans-4-(trans-4-ethylcyclohexyl)cyclohexyl)ethyl)cyclohexyl)-(4-fluorobutyl)benzene(in general formula (1), R is C₂H₅, m is 4, X is F, A₁, A₂ and A₃ aretrans-1,4-cyclohexylene groups, A₄ is a 1,4-phenylene group, both Z₁ andZ₃ are covalent bonds, Z₂ is —(CH₂)₂—)(No. 149)

4-(trans-4-(2-(trans-4-ethylcyclohexyl)cyclohexyl)ethyl)cyclohexyl)-(4-hydroxybutyl)benzene4.4 g (0.010 mol) and dichloromethane 45 ml were mixed.

To the mixture, a solution of DAST 2.4 g (0.015 mol) in dichloromethane5 ml were added dropwise to maintain the temperature at −50° C., andstirred for 30 minutes at the same temperature. Then, the temperaturewas increased slowly and the mixture was stirred for 5 hours at roomtemperature.

The reaction mixture was poured into ice water 100 ml and extracted withdichloromethane 90 ml. The obtained organic phase was washed with waterthree times and dried over anhydrous magnesium sulfate. The solvent wasdistilled out under reduced pressure, and the residue waschromatographed over silica gel (elute: toluene/heptane) to obtain 3.9 gof crude4-(trans-4-(2-(trans-4-(trans-4-ethylcyclohexyl)cyclohexyl)ethyl)cyclohexyl)-(4-fluorobutyl)benzene.The resulting compound was recrystallized from ethyl acetate, and 1.9 gof the title compound (yield: 43.2%) was obtained.

Moreover, the structure was supported by each spectrum data.

Mass spectrometric analysis: 454 (M⁺)

¹H-NMR (CDCl₃, TMS internal standard)

δ (ppm)

0.69-2.53 (m, 45H)

4.45 (dt, 2H)

7.10 (s, 4H)

The following compounds are prepared according to the above method ofExample 5 (No.150-No.205).

No.

1504-(trans-4-(2-(trans-4-(trans-4-methyleyclohexyl)cyclohexyl)ethyl)cyclohexyl)-(3-fluoropropyl)benzene

1514-(trans-4-(2-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)ethyl)cyclohexyl)-(5-fluoropentyl)benzene

1524-(trans-4-(2-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)ethyl)cyclohexyl)-fluoromethylbenzene

1534-(trans-4-(2-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)ethyl)cyclohexyl)-(2-fluoroethyl)benzene

1544-(trans-4-(2-(trans-4-(trans-4-butylcyclohexyl)cyclohexyl)ethyl)cyclohexyl)-fluoromethylbenzene

1554-(trans-4-(2-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)ethyl)cyclohexyl)-fluoromethylbenzene

1564-(trans-4-(2-(trans-4-(trans-4-nonylcyclohexyl)cyclohexyl)ethyl)cyclohexyl)-fluoromethylbenzene

157(Z)-4-(trans-4-(2-(trans-4-(trans-4-(2-pentenyl)cyclohexyl)cyclohexyl)ethyl)cyclohexyl)-(3-fluoropropyl)benzene

1584-(trans-4-(2-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)ethyl)cyclohexyl)-(4-chlorobutyl)benzene

1594-(trans-4-(2-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)ethyl)cyclohexyl)-(4-chlorobutyl)benzene

1604-methyl-(trans-4-(2-(trans-4-(trans-4-fluoromethylcyclohexyl)cyclohexyl)ethyl)cyclohexyl)benzene

1614-propyl-(trans-4-(2-(trans-4-(trans-4-(2-fluoroethyl)cyclohexyl)cyclohexyl)ethyl)cyclohexyl)benzene

1624-pentyl-(trans-4-(2-(trans-4-(trans-4-(5-fluoropentyl)cyclohexyl)cyclohexyl)ethyl)cyclohexyl)benzene

1634-methoxybutyl-(trans-4-(2-(trans-4-(trans-4-(3-fluoropropyl)cyclohexyl)cyclohexyl)ethyl)cyclohexyl)benzene

1644-(trans-4-(trans-4-(trans-4-ethylcyclohexyl)cyclohexyl)cyclohexyl)-(2-fluoroethyl)benzene

1654-(trans-4-(trans-4-(trans-4-ethylcyclohexyl)cyclohexyl)cyclohexyl)-(3-fluoropropyl)benzene

1664-(trans-4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)cyclohexyl)-fluoromethylbenzene

167 4-(trans-4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)cyclohexyl)-(4-fluorobutyl)benzene

1684-(trans-4-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)cyclohexyl)-fluoromethylbenzene

1694-(trans-4-(trans-4-(trans-4-ethenylcyclohexyl)cyclohexyl)cyclohexyl)-(5-fluoropentyl)benzene

1704-(trans-4-(trans-4-(trans-4-methylcyclohexyl)cyclohexyl)cyclohexyl)-(4-chlorobutyl)benzene

171 4-(trans-4-(trans-4-(trans-4-(3-butenyl)cyclohexyl)cyclohexyl)cyclohexyl)-(3-fluoropropyl)benzene

1724-methyl-(trans-4-(trans-4-(trans-4-(3-fluoropropyl)cyclohexyl)cyclohexyl)cyclohexyl)benzene

1734-ethyl-(trans-4-(trans-4-(trans-4-(3-fluoropropyl)cyclohexyl)cyclohexyl)cyclohexyl)benzene

1744-propyl-(trans-4-(trans-4-(trans-4-(4-fluorobutyl)cyclohexyl)cyclohexyl)cyclohexyl)benzene

1754-propyl-(trans-4-(trans-4-(trans-4-(5-fluoropentyl)cyclohexyl)cyclohexyl)cyclohexyl)benzene

1764-butyl-(trans-4-(trans-4-(trans-4-(4-fluorobutyl)cyclohexyl)cyclohexyl)cyclohexyl)benzene

1774-heptyl-(trans-4-(trans-4-(trans-4-(8-fluorooctyl)cyclohexyl)cyclohexyl)cyclohexyl)benzene

178(E)-4-(3-pentenyl)-(trans-4-(trans-4-(trans-4-(2-fluoroethyl)cyclohexyl)cyclohexyl)cyclohexyl)benzene

1794-pentyloxy-(trans-4-(trans-4-(trans-4-(4-fluorobutyl)cyclohexyl)cyclohexyl)cyclohexyl)benzene

1804-(2-(trans-4-(trans-4-(trans-4-ethylcyclohexyl)cyclohexyl)cyclohexyl)ethyl)-(2-fluoroethyl)benzene

181 4-(2-(trans-4-(trans-4-(trans-4-ethylcyclohexyl)cyclohexyl)cyclohexyl)ethyl)-(4-fluorobutyl)benzene

1824-(2-(trans-4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)cyclohexyl)ethyl)-fluoromethylbenzene

1834-(2-(trans-4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)cyclohexyl)ethyl)-(2-fluoroethyl)benzenefluoromethylbenzene

1844-(2-(trans-4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)cyclohexyl)ethyl)-(4-fluorobutyl)benzene

1854-(2-(trans-4-(trans-4-(trans-4-butylcyclohexyl)cyclohexyl)cyclohexyl)ethyl)-fluoromethylbenzene

1864-(2-(trans-4-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)cyclohexyl)ethyl)-fluoromethylbenzene

1874-(2-(trans-4-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)cyclohexyl)ethyl)-(3-fluoropropyl)benzene

188(E)-4-(2-(trans-4-(trans-4-(trans-4-(1-propenyl)cyclohexyl)cyclohexyl)cyclohexyl)ethyl)-(5-fluoropentyl)benzene

1894-ethyl-(2-(trans-4-(trans-4-(trans-4-(3-fluoropropyl)cyclohexyl)cyclohexyl)cyclohexyl)ethyl)benzene

1904-propyl-(2-(trans-4-(trans-4-(trans-4-(5-fluoropentyl)cyclohexyl)cyclohexyl)cyclohexyl)ethyl)benzene

1914-butyl-(2-(trans-4-(trans-4-(trans-4-(4-fluorobutyl)cyclohexyl)cyclohexyl)cyclohexyl)ethyl)benzene

192 (E)-4-(1-butenyl)-(2-(trans-4-(trans-4-(trans-4-(2-fluoroethyl)cyclohexyl)cyclohexyl)cyclohexyl)ethyl)benzene

1934-methoxypentyl-(2-(trans-4-(trans-4-(trans-4-(6-fluorohexyl)cyclohexyl)cyclohexyl)cyclohexyl)ethyl)benzene

1944-(trans-4-(trans-4-(2-(trans-4-propylcyclohexyl)ethyl)cyclohexyl)cyclohexyl)-fluoromethylbenzene

1954-(trans-4-(trans-4-(2-(trans-4-butylcyclohexyl)ethyl)cyclohexyl)cyclohexyl)-(5-fluoropentyl)benzene

1964-(trans-4-(trans-4-(2-(trans-4-heptylcyclohexyl)ethyl)cyclohexyl)cyclohexyl)-(2-fluoroethyl)benzene

1974-(trans-4-(trans-4-(2-(trans-4-ethoxyethylcyclohexyl)ethyl)cyclohexyl)cyclohexyl)-(3-fluoropropyl)benzene

1984-methyl-(trans-4-(trans-4-(2-trans-4-(5-fluoropentyl)cyclohexyl)ethyl)cyclohexyl)cyclohexyl)benzene

1994-propyl-(trans-4-(trans-4-(2-(trans-4-(4-fluorobutyl)cyclohexyl)ethyl)cyclohexyl)cyclohexyl)benzene

2004-pentyl-(trans-4-(trans-4-(2-(trans-4-(5-fluoropentyl)cyclohexyl)ethyl)cyclohexyl)cyclohexyl)benzene

2014-(2-propenyl)-(trans-4-(trans-4-(2-trans-4-(3-fluoropropyl)cyclohexyl)ethyl)cyclohexyl)cyclohexyl)benzene

202 2-fluoro-4-(trans-4-(2-(trans-4-(trans-4-ethylcyclohexyl)cyclohexyl)ethyl)cyclohexyl)-(2-fluoroethyl)benzene

2032,6-difluoro-4-(trans-4-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)cyclohexyl)-(3-fluoropropyl)benzene

2042-fluoro-4-propyl-(trans-4-(trans-4-(trans-4-(5-fluoropentyl)cyclohexyl)cyclohexyl)cyclohexyl)benzene

2053-fluoro-(2-(trans-4-(trans-4-(trans-4-methylcyclohexyl)cyclohexyl)cyclohexyl)ethyl)-fluoromethylbenzene

EXAMPLE 6

Preparation of 4-(trans-4-(2-fluoroethyl)cyclohexyl)-4″-ethyl-1,1′:4′,1″-terphenyl (in general formula (1), R is C₂H₅, m is 2, X is F,A₁, A₂ and A₃ are 1,4-phenylene groups, A₄ is a trans-1,4-cyclohexylenegroup, Z₁, Z₂ and Z₃ are covalent bonds)(No. 206)

4-(trans-4-(2-hydroxyethyl)cyclohexyl)-4″-ethyl-1,1′:4′,1″-terphenyl 4.8g (0.013 mol) and dichloromethane 50 ml were mixed. To the mixture, asolution of DAST 3.0 g (0.019 mol) in dichloromethane 6 ml were addeddropwise to maintain the temperature at -50 ° C, and stirred for 30minutes at the same temperature. Then, the temperature was increasedslowly and the mixture was stirred for 5 hours at room temperature.

The reaction mixture was poured into ice water 100 ml and extracted withdichloromethane 100 ml.

The obtained organic phase was washed with water three times and driedover anhydrous magnesium sulfate.

The solvent was distilled out under reduced pressure, and the residuewas chromatographed over silica gel (elute: toluene/heptane) to obtain4.3 g of crude4-(trans-4-(2-fluoroethyl)cyclohexyl)-4″-ethyl-1,1′:4′,1″-terphenyl. Theresulting compound was recrystallized from ethyl acetate, and 1.7 g thetitle compound (yield: 35.4%) was obtained.

Moreover, the structure was supported by each spectrum data.

Mass spectrometric analysis: 386 (M⁺)

¹H-NMR (CDCl₃, TMS internal standard)

δ (ppm)

0.80-2.76 (m, 27H)

4.44 (dt, 2H)

7.30-7.75 (m, 12H)

The following compounds are prepared according to the above method ofExample 6 (No.207-No.247).

No.

207 4-(trans-4-(3-fluoropropyl)cyclohexyl)-4″-ethyl-1,1′:4′,1″-terphenyl

208 4-(trans-4-(4-fluorobutyl)cyclohexyl)-4″-propyl-1,1′:4′,1″-terphenyl

209 4-(trans-4-(2-fluoroethyl)cyclohexyl)-4″-pentyl-1,1′:4′,1″-terphenyl

210⁴-(trans-4-(4-fluorobutyl)cyclohexyl)-4″-heptyloxy-1,1′:4′,1″-terphenyl

2114-(3-fluoropropyl)-4″-(trans-4-methylcyclohexyl)-1,1′:4′,1″-terphenyl

212 4-(5-fluoropentyl)-4″-(trans-4-ethylcyclohexyl)-1,1′:4′,1″-terphenyl

213 4-(4-fluorobutyl)-4″-(trans-4-propylcyclohexyl)-1,1′:4′,1″-terphenyl

214 4-(4-fluorobutyl)-4″-(trans-4-butylcyclohexyl)-1,1′:4′,1″-terphenyl

215 4-(5-fluoropentyl)-4″-(trans-4-pentylcyclohexyl)-1,1′:4′,1″-terphenyl

216 4-(4-fluoromethyl)-4″-(trans-4-decylcyclohexyl)-1,1′:4′,1″-terphenyl

2174-(7-fluoroheptyl)-4″-(trans-4-(4-pentenyl)cyclohexyl)-1,1′:4′,1″-terphenyl

218 4-(3-chloropropyl)-4″-(trans-4-butylcyclohexyl)-1,1′:4′,1″-terphenyl

2194-(trans-4-(4-fluorobutyl)cyclohexyl)-4′-(2-(4-ethylphenyl)ethyl)biphenyl

2204-(trans-4-(3-fluoropropyl)cyclohexyl)-4′-(2-(4-propylphenyl)ethyl)biphenyl

2214-(trans-4-(6-fluorohexyl)cyclohexyl)-4′-(2-(4-butylphenyl)ethyl)biphenyl

2224-(trans-4-(2-fluoroethyl)cyclohexyl)-4′-(2-(4-hexylphenyl)ethyl)biphenyl

223(Z)-4-(trans-4-(4-fluoromethylcyclohexyl)-4′-(2-(4-(4-hexenyl)phenyl)ethyl)biphenyl

2244-(2-(trans-4-(4-fluorobutyl)cyclohexyl)ethyl)-4″-propyl-1,1′:4′,1″-terphenyl

2254-(2-(trans-4-(5-fluoropentyl)cyclohexyl)ethyl)-4″-pentyl-1,1′:4′,1″-terphenyl

2264-(2-(trans-4-(2-fluoroethyl)cyclohexyl)ethyl)-4″-heptyl-1,1′:4′,1″-terphenyl

2274-(2-(trans-4-(3-fluoropropyl)cyclohexyl)ethyl)-4″-propoxymethyl-1,1′:4′,1″-terphenyl

2284-(2-(4-(5-fluoropentyl)phenyl)ethyl)-4′-(trans-4-methylcyclohexyl)biphenyl

2294-(2-(4-(2-fluoroethyl)phenyl)ethyl)-4′-(trans-4-ethylcyclohexyl)biphenyl

2304-(2-(4-fluoromethylphenyl)ethyl)-4′-(trans-4-nonylcyclohexyl)biphenyl

231 (E) -4-(2-(4- (3-fluoropropyl)phenyl) ethyl)-4′-(trans-4-(1-butenyl)cyclohexyl)biphenyl

2324-(2-fluoroethyl)-4″-(2-(trans-4-propylcyclohexyl)ethyl)-1,1′:4′,1″-terphenyl

2334-(5-fluoropentyl)-4″-(2-(trans-4-propylcyclohexyl)ethyl)-1,1′:4′,1″-terphenyl

2344-(3-fluoropropyl)-4″-(2-(trans-4-heptylcyclohexyl)ethyl)-1,1′:4′,1″-terphenyl

2354-(4-fluorobutyl)-4″-(2-(trans-4-methoxymethylcyclohexyl)ethyl)-1,1′:4′,1″-terphenyl

236 4-(2-(4-(trans-4-(3-fluoropropyl)cyclohexyl)phenyl)ethyl)-4′-methylbiphenyl

2374-(2-(4-(trans-4-(5-fluoropentyl)cyclohexyl)phenyl)ethyl)-4′-ethylbiphenyl

238 4-(2-(4- (trans-4-(2-fluoroethyl)cyclohexyl)phenyl)ethyl)-4′-octylbiphenyl

2394-fluoromethyl-4′-(2-(4-(trans-4-ethylcyclohexyl)phenyl)ethyl)biphenyl

2404-(4-fluorobutyl)-4′-(2-(4-(trans-4-ethylcyclohexyl)phenyl)ethyl)biphenyl

2414-(6-fluorohexyl)-4′-(2-(4-(trans-4-hexylcyclohexyl)phenyl)ethyl)biphenyl

2424-(3-fluoropropyl)-4′-(2-(4-(trans-4-(4-pentenyl)cyclohexyl)phenyl)ethyl)biphenyl

2432-fluoro-4-(trans-4-(4-fluorobutyl)cyclohexyl)-2′-fluoro-4″-butyl-1,1′:4′,1″-terphenyl

2443-fluoro-4-(5-fluoropentyl)-2′-fluoro-2″-fluoro-4′″-(trans-4-ethylcyclohexyl)-1,1′:4′,1″-terphenyl

2454-(2-(2-fluoro-4-(trans-4-(3-fluoropropyl)cyclohexyl)phenyl)ethyl)-4′-methylbiphenyl

2464-fluoromethyl-3′-fluoro-4′-(2-(2-(fluoro-4-(trans-4-propylcyclohexyl)phenyl)ethyl)biphenyl

2474-chloromethyl-3′-fluoro-4′-(2-(2-fluoro-4-(trans-4-propylcyclohexyl)phenyl)ethyl)biphenyl

248 2-(4-(trans-4-(5-fluoropentyl)cyclohexyl)phenyl)-5-(4-propylphenyl)pylimidine

2492-(trans-4-(4′-(3-fluoropropyl)biphenyl-4-yl)cyclohexyl)-5-pentyldioxane

In the following, the use of the compounds of the present invention asconstituents of liquid crystal compositions are exemplified. In each useexamples, NI shows nematic phase-isotropic phase transition temperature(° C.), Δ ε shows a dielectric anisotropy value, Δ n shows a refractiveindex anisotropy value, η shows a viscosity at 20° C. (mPa.s) and V₁₀shows a threshold voltage (V).

EXAMPLE 7 (use example 1)

Liquid crystal composition containing the following compound of acyanophenylcyclohexane type:

4-(trans-4-propylcyclohexyl)benzonitrile 24% by weight4-(trans-4-pentylcyclohexyl)benzonitrile 36% by weight4-(trans-4-heptylcyclohexyl)benzonitrile 25% by weight4-(trans-4-pentylcyclohexyl)-4′-cyanobiphenyl 15% by weight

The above composition has the following values of physical properties.

NI: 72.4, Δε: 11.0, Δ n: 0.137, η: 27.2, V₁₀: 1.78 at cell thickness 9μm.

To 85% by weight of the composition, 15% by weight of4-(trans-4-(4-fluorobutyl)cyclohexyl)-4′-(trans-4-butylcyclohexyl)biphenyl(compound No. 1) was mixed to obtain a nematic liquid crystalcomposition. The values of physical properties of this liquid crystalcomposition is as follows.

NI: 98.6, Δ ε: 9.9, Δ n: 0.141, η: 33.5, V₁₀: 1.94 at cell thickness 8.7μm.

Although the composition had been left at −20° C. in a freezer, nocrystal were found in over 60 days.

EXAMPLE 8 (use example 2)

The same procedure as in Example 7 was repeated except that4-(trans-4-(4-fluorobutyl)cyclohexyl)-4′-(trans-4-butylcyclohexyl)biphenyl(compound No. 1) was changed to4-(trans-4-(5-fluoropentyl)cyclohexyl)-4′-(trans-4-ethenylcyclohexyl)biphenyl(compound No. 15). The values of physical properties of this liquidcrystal composition are as follows.

NI: 99.8, Δ ε: 9.7, Δ n: 0.143, 7) : 33.1, V₁₀: 1.98 at cell thickness8.7 μm.

Although the composition had been left at −20° C. in a freezer, nocrystals were found in over 60 days.

EXAMPLE 9 (use example 3)

The values of physical properties of the liquid crystal composition ofcomposition example 23 are as follows.

NI: 96.6, Δ ε: 7.1, Δ n: 0.162, η:17.0, V₁₀: 2.10.

EXAMPLE 10 (use example 4)

The values of physical properties of the liquid crystal composition ofcomposition example 24 are as follows.

NI: 93.2, Δ ε: 8.7, Δ n : 0.149, η: 19.8, V₁₀: 1.99.

EXAMPLE 11 (use example 5)

The values of physical properties of the liquid crystal composition ofcomposition example 25 are as follows.

NI: 97.7, Δ ε: 30.9, Δ n: 0.147, η: 89.1, V₁₀: 0.86.

EXAMPLE 12 (use example 6)

The values of physical properties of the liquid crystal composition ofcomposition example 26 are as follows.

NI: 103.6, Δ ε: 6.4, Δ n : 0.198, η: 39.5, V₁₀: 2.28.

EXAMPLE 13 (use example 7)

The values of physical properties of the liquid crystal composition ofcomposition example 27 are as follows.

NI: 72.3, Δ ε: 11.5, Δ n: 0.122, η: 40.9, V₁₀: 1.30.

EXAMPLE 14 (use example 8)

The values of physical properties of the liquid crystal composition ofcomposition example 28 are as follows.

NI: 84.7, Δ ε: 8.1, Δ n: 0.141, η: 20.0, V₁₀: 1.75.

EXAMPLE 15 (use example 9)

The values of physical properties of the liquid crystal composition ofcomposition example 29 are as follows.

NI: 84.6, Δ: 23.5, Δ n: 0.118, η: 39.0, V₁₀: 0.99.

EXAMPLE 16 (use example 10)

The values of physical properties of the liquid crystal composition ofcomposition example 30 are as follows.

NI: 93.6, Δ ε: 28.2, Δ n : 0.140, η: 41.6, V₁₀:1.00.

EXAMPLE 17 (use example 11)

The values of physical properties of the liquid crystal composition ofcomposition example 31 are as follows.

NI: 68.1, Δε: 9.9, Δ n : 0.115, η: 28.8, V₁₀: 1.36.

EXAMPLE 18 (use example 12)

The values of physical properties of the liquid crystal composition ofcomposition example 32 are as follows.

NI: 76.3, Δε: 6.5, Δ n : 0.164, η: 24.3, V₁₀: 1.78.

EXAMPLE 19 (use example 13)

The values of physical properties of the liquid crystal composition ofcomposition example 33 are as follows.

NI: 106.7, Δ ε: 5.0, Δ n : 0.097, η: 27.6, V₁₀: 2.22.

EXAMPLE 20 (use example 14)

The values of physical properties of the liquid crystal composition ofcomposition example 34 are as follows.

NI:96.4, Δ ε:3.2, Δn:0.096, η:22.5, V₁₀:2.69.

EXAMPLE 21 (use example 15)

The values of physical properties of the liquid crystal composition ofcomposition example 35 are as follows.

NI: 93.4, Δ ε: 5.7, Δ n : 0.120, η: 27.6, V₁₀: 2.00.

EXAMPLE 22 (use example 16)

The values of physical properties of the liquid crystal composition ofcomposition example 36 are as follows.

NI: 83.0, Δ ε: 8.4, Δ n 0.090, η: 29.9, V₁₀:1.60.

EXAMPLE 23 (use example 17)

The values of physical properties of the liquid crystal composition ofcomposition example 37 are as follows.

NI: 94.7, Δ ε: 4.8, Δ n: 0.125, η:22.4, V₁₀: 2.34.

EXAMPLE 24 (use example 18)

The values of physical properties of the liquid crystal composition ofcomposition example 38 are as follows.

NI: 99.3, Δε : 8.9, Δ n : 0.116, η:35.2, V₁₀:1.77.

EXAMPLE 25 (use example 19)

The values of physical properties of the liquid crystal composition ofcomposition example 39 are as follows.

NI: 89.4, Δ ε: 4.5, Δ n : 0.093, η:15.8, V₁₀: 2.40.

EXAMPLE 26 (use example 20)

The values of physical properties of the liquid crystal composition ofcomposition example 40 are as follows.

NI: 81.1, Δ ε: 8.2, Δ n: 0.095, η: 28.7, V₁₀:1.75.

EXAMPLE 27 (use example 21)

The values of physical properties of the liquid crystal composition ofcomposition example 41 are as follows.

NI: 95.9, Δ ε: 7.3, Δ n : 0.134, η:35.3, V₁₀: 1.91.

Moreover, although the liquid crystal compositions in the above examples9-27 had been left at −20° C. in a freezer, no crystal were found inover 60 days.

EXAMPLE 28 (use example 22)

To 85% by weight of mother liquid crystal composition (a) containing3,4-difluoro-(trans-4-(trans-4-ethylcyclohexyl)cyclohexyl)benzene, 3,4-difluoro-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)benzene and3,4-difluoro-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)benzene,which are liquid crystal compounds of a fluorine type, at the sameweight, 15% by weight of4-(trans-4-(4-fluorobutyl)cyclohexyl)-4′-(trans-4-butylcyclohexyl)biphenyl(compound No. 1), or 4, 4′-bis (trans-4-butylcyclohexyl)biphenyl forcomparison, or4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)benzonitrile,respectively, was mixed to obtain nematic composition (b), (c) and (d).

The temperature change of voltage holding rates (%) of these liquidcrystal compositions is measured and the results are shown in FIG. 1.

Furthermore, the vertical axis shows the voltage holding rate and thehorizontal axis shows the temperature measured (° C.).

As shown in the figure, liquid crystal composition (b) of the presentinvention shows a high voltage holding rate in the region of measuredtemperatures. From the results, it is known that the composition can beused as a necessary liquid crystal composition for TFT.

COMPARISON EXAMPLE 1

The same procedure as in Example 7 was repeated except that4-(trans-4-(4-fluorobutyl)cyclohexyl)-4′-(trans-4-butylcyclohexyl)biphenyl(compound No. 1) was changed to 4,4′-bis(trans-4-butylcyclohexyl)biphenyl which is a comparative compoundhaving the same structure but not substited by fluorine. The values ofphysical properties of this liquid crystal composition are as follows.

NI: 98.8, Δ ε:9.6, Δ n: 0.140, η:33.3, V₁₀: 2.00 at cell thickness 8.7μm.

Although the composition had been left at −20° C. in a freezer, crystalwere at 34 days.

From the results, compared the compounds of the present invention withthe compounds of comparative examples, it is known that the lowering oftransition temperatures of isotropic phases and the increase ofviscosity are controlled to the same extent, but the compatibility ofthe former compound is more improved than the latter compound.

As described above, the compounds of the present invention have veryexcellent stability, and it can improve the compatibility with the otherliquid crystal materials during a high transition temperature of theisotropic phase and low viscosity are held.

INDUSTRIAL APPLICABILITY

Accordingly, when the compounds of the present invention are used asconstituents of liquid crystal compositions, such compounds haveexcellent compatibility with the other liquid crystal materials, and itis possible to provide new liquid crystal compounds having desiredphysical properties by selecting six rings, substituent groups and/orbonding groups of molecular-constituting elements.

What is claimed is:
 1. A liquid crystalline compound which isrepresented by the formula (1): R—A₁—Z₁—A₂—Z₂—A₃—Z₃—A₄—(CH₂)_(m).X  (1)wherein R indicates H or an alkyl group having 1 to 10 carbon atoms (oneor more methylene groups (—CH₂—) in the alkyl group may be replaced by—O—, —S—, —CO—; —CH═CH— or —C≡C—, but —O— or —S— are not continuous), mindicates an integer of 1 to 10; X indicates F, Cl, Br, I or OH; A₁, A₂,A₃, and A₄, each independently indicate a trans 1,4-cyclohexylene group,a 1,4-phenylene group with the proviso that when at least two of A₁, A₂,A₃, and A₄ are 1, 4-phenylene groups, one of A₁, A₂, A₃, and A₄ may haveone hydrogen substituted by a fluorine atom, cyclohexenylenediyl group,a pyrimidine-2,5-diyl group, a pyridine-2,5-diyl group or a1,3-dioxane-2,5-diyl group; Z₁, Z₂ and Z₃, each independently, indicate—(CH₂)₂— or a covalent bond, and at least two of Z₁, Z₂, and Z₃,indicated covalent bond; with the proviso that A₂ to A₄ are never allcyclohexylene groups.
 2. A liquid crystalline compound according toclaim 1, wherein X is F.
 3. A liquid crystalline compound according toclaim 1, wherein X is OH.
 4. A liquid crystalline compound according toclaim 2, wherein Z₁, Z₂ and Z₃ are covalent bonds.
 5. A liquidcrystalline compound according to claim 2, wherein Z₁ is —(CH₂)₂—.
 6. Aliquid crystalline compound according to claim 2, wherein Z₂ is—(CH₂)₂—.
 7. A liquid crystalline compound according to claim 2, whereinZ₃ is —(CH₂)₂—.
 8. A liquid crystalline compound according to claim 4,wherein both A₁ and A₄ are the trans 1,4-cyclohexylene group, and bothA₂ and A₃ are the 1,4-phenylene group in which one or more hydrogenatoms on the ring may be substituted by a fluorine atom.
 9. A liquidcrystalline compound according to claim 4, wherein both A₁ and A₂ arethe 1,4-phenylene group in which one or more hydrogen atoms on the ringmay be substituted by a fluorine atom, and both A₃ and A₄ are the trans1,4-cyclohexylene group.
 10. A liquid crystalline compound according toclaim 6, wherein both A₁ and A₂ are the 1,4-phenylene group in which oneor more hydrogen atoms on the ring may be substituted by a fluorineatom, and both A₃ and A₄ are the trans 1,4-cyclohexylene group.
 11. Aliquid crystal composition comprising at least one of liquid crystallinecompounds according to claim
 1. 12. A liquid crystal composition,characterized in that it comprises a first constituent comprising atleast one compound selected from the group consisting of the liquidcrystalline compounds described in claim 1 and a second constituentcomprising at least one compound selected from the group consisting ofthe compounds represented by formulas (2), (3) and (4):

wherein R₁ indicates an alkyl group having 1 to 10 carbon atoms; X₁indicates F, Cl, OCF₃, OCF₂H, CF₂H or CFH₂; L₁, L₂, L₃ and L₄, eachindependently indicate H or F; Z, and Z,, each independently, indicate—(CH₂)₂—, —CH═CH—, or a covalent bond, and a indicates 1 or
 2. 13. Aliquid crystal composition, characterized in that it comprises a firstconstituent comprising at least one compound selected from the groupconsisting of the liquid crystalline compounds described in claim 1 anda second constituent comprising at least one compound selected from thegroup consisting of the compounds represented by formulas (5), (6), (7),(8) and (9):

wherein R₂ indicates F, an alkyl group having 1 to 10 carbon atoms or analkenyl group having 2 to 10 carbon atoms; any methylene group (—CH₂—)in the alkyl group or the alkenyl group may be replaced by an oxygenatom, but two or ore methylene groups are not continuously replaced bythe oxygen atom; ring A indicates a trans-1,4-cyclohexylene group, a1,4-phenylene group or a 1,3-dioxane-2,5-diyl group; ring B indicates atrans-1,4-cyclohexylene group, a 1,4-phenylene group or apyrimidine-,5-diyl group; ring C indicates a trans-1,4-cyclohexylenegroup or a 1,4-phenylene group; Z₆ indicates —(CH₂)₂—, —COO— or acovalent bond; L₅ and L₆, each independently, indicate H or F; and b andc, each independently, indicate 0 or 1,

wherein R₃ indicates an alkyl group having 1 to 10 carbon atoms, L₇indicates H or F; and d indicates 0 or 1,

wherein R₄ indicates an alkyl group having 1 to 10 carbon atoms; ring Dand ring E, each independently, indicate trans-1,4-cyclohexylene groupor a 1,4-phenylene group; Z₇ and Z₈, each independently, indicate —COO—or a covalent bond; Z₉ indicates —COO— or —C≡C—; L₈ and L₉, eachindependently, indicate H or F; X₂ is F, OCF₃, OCF₂H, CF₃, CF₂H or CFH₂;when X₂ indicates OCF₃, OCF₂H, OCF₂H, CF₃, CF₂H or CFH₂, L₈ and L₉ bothindicate H; e, f and g, each independently, indicates 0 or 1,

wherein R₅ and R₆, each independently, indicate an alkyl group having 1to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, andin any case, any methylene group (—CH₂—) may be replaced by an oxygenatom (—O—), but two or more methylene groups are not continuouslyreplaced by an oxygen atom; ring G indicates a trans-1,4-cyclohexylenegroup, a 1,4-phenylene group or a pyrimidine-2,5-diyl group; ring Hindicates a trans-1,4-cyclohexylene group or a 1,4-phenylene group; Z₁₀indicates —(CH₂)₂—, —COO—, —CH≡CH—C═C— or a covalent bond; Z₁₁ indicates—COO— or a covalent bond, and

wherein R₇ and R₈, each independently, indicate an alkyl group having 1to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, andin any case, any methylene group (—CH₂—) may be replaced by an oxygenatom (—O—), but two or more methylene groups are not continuouslyreplaced by an oxygen atom; ring I indicates a trans-1,4-cyclohexylenegroup, a 1,4-phenylene group or a pyrimidine-2,5-diyl group; ring Jindicates a trans-1,4-cyclohexylene group, a 1,4-phenylene group inwhich one or more hydrogen atoms on the ring may be substituted by afluoric atom, or a pyrimidine-2,5-dyl group; ring K indicates atrans-1,4-cyclohexylene group or a 1,4-phenylene group, Z₁₂ and Z₁₄,each independently, indicate —COO—, —(CH₂)₂— or a covalent bond, Z₁₃indicates —CH═CH—, —C—C—, —COO— or a covalent bond; and h indicates 0or
 1. 14. A liquid crystal composition, characterized in that itcomprises comprising at least one compound selected from the groupconsisting of the liquid crystalline compounds described in claim 1, anda second constituent comprising at least one compound selected from thegroup consisting of the compounds represented by formulas (2), (3) and(4):

wherein R₁ indicates an alkyl group having 1 to 10 carbon atoms; X,indicates F, Cl, OCF₃, OCF₂H, CF₂H or CFH₂; L₁, L₂, L₃ and L₄, eachindependently indicate H or F; Z₄ and Z₅, each independently, indicate—(CH₂)₂—, —CH═CH—, or a covalent bond, and a indicates 1 or 2, and atleast one compound selected from the group consisting of the compoundsrepresented by formulas (5), (6), (7), (8) and (9):

wherein R₃ indicates F, an alkyl group having 1 to 10 carbon atoms or analkenyl group having 2 to 10 carbon atoms; any methylene group (—CH₃—)in the alkyl group or the alkenyl group may be replaced by an oxygenatom, but two or ore methylene groups are not continuously replaced bythe oxygen atom; ring A indicates a trans-1,4-cyclohexylene group, a1,4-phenylene group or a 1,3-dioxane-2,5-diyl group; ring B indicates atrans-1,4-cyclohexylene group, a 1,4-phenylene group or apyrimidine-,5-diyl group; ring C indicates a trans-1,4-cyclohexylenegroup or a 1,4-phenylene group; Z₆ indicates —(CH₂)₃—, —COO— or acovalent bond; L₅ and L₆, each independently, indicate R or F; and b andc, each independently, indicate 0 or 1,

wherein R₃ indicates an alkyl group having 1 to 10 carbon atoms, L₇indicates H or F; and d indicates 0 or 1,

wherein R₄ indicates an alkyl group having 1 to 10 carbon atoms; ring Dand ring E, each independently, indicate trans-1,4-cyclohexylene groupor a 1,4-phenylene group; Z₇ and Z₈, each independently, indicate —COO—or a covalent bond; Z₉ indicates —COO— or —C≡C—; L₈ and L₉, eachindependently, indicate H or F; X₂ is F, OCF₃, OCF₂H, CF₃, CF₃H or CFH₂;when X₂ indicates OCF₃, OCF₂H, OCF₃H, CF₃, CF₃H or CFH₂, L₈ and L₉ bothindicate H; e, f and g, each independently, indicates 0 or 1,

wherein R₅ and R₆, each independently, indicate an alkyl group having 1to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, andin any case, any methylene group (—CH₂—) may be replaced by an oxygenatom (—O—), but two or more methylene groups are not continuouslyreplaced by an oxygen atom; ring G indicates a trans-1,4-cyclohexylenegroup, a 1,4-phenylene group or a pyrimidine-2,5-diyl group; ring Hindicates a trans-1,4-cyclohexylene group or a 1,4-phenylene group; Z₁₀indicates —(CH₂)₂—, —COO—, —CH═CH—C≡C— or a covalent bond; Z₁₄ indicates—COO— or a covalent bond, and

wherein R₇ and R₈, each independently, indicate an alkyl group having 1to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, andin any case, any methylene group (—CH₂—) may be replaced by an oxygenatom (—O—), but two or more methylene groups are not continuouslyreplaced by an oxygen atom; ring I indicates a trans-1,4-cyclohexylenegroup, a 1,4-phenylene group or a pyrimidine-2,5-diyl group; ring Jindicates a trans-1,4-cyclohexylene group, a 1,4-phenylene group inwhich one or more hydrogen atoms on the ring may be substituted by afluoric atom, or a pyrimidine-2,5-dyl group; ring K indicates atrans-1,4-cyclohexylene group or a 1,4-phenylene group, Z₁₂ and Z₁₄,each independently, indicate —COO—, —(CH₂)₂— or a covalent bond, Z₁₃indicates —CH═CH—, —C≡C—, —COO— or a covalent bond; and h indicates 0or
 1. 15. A liquid crystal display device comprising the liquid crystalcompositions described in claim
 11. 16. A liquid crystal display devicecomprising the liquid crystal compositions described in claim
 12. 17. Aliquid crystal display device comprising the liquid crystal compositionsdescribed in claim
 13. 18. A liquid crystal display device comprisingthe liquid crystal compositions described in claim 14.